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1 Introduction
1.1 M
embrane-based water treatment
processes
Long-range predictions of water supply and demand
predict that more than 40% of the worlds population is
likely to be living under severe water stress by 2050, with
global water demand projected to increase by 55% between
2000 and 2050 (Marchal etal. 2012). In populated, waterscarce regions limited by natural water resources, seawater and wastewater are used as potable water resources
but require extensive treatment before being suitable for
drinking (Shannon et al. 2008). The separation of water
from salt and other contaminants is most commonly done
through membrane separation processes (van der Bruggen
etal. 2003). Membranes are semipermeable barriers that
provide selectivity in response to a physical or chemical
potential gradient (e.g. pressure, concentration gradients,
and electric fields) (Buonomenna 2013). Membranes can
be divided into dense materials (reverse osmosis [RO]
and nanofiltration [NF]) or porous materials (microfiltration [MF] and ultrafiltration [UF]) (Kennedy et al. 2008).
Although UF and MF are mainly used for the filtration of
submicron-sized particles and organic material, NF and
RO are used for the desalination and removal of small
charged organic molecules (van der Bruggen etal. 2003).
The fastest growing desalination technology is RO, where
water is transported through a dense membrane that is
impermeable to ions, in response to a pressure gradient.
1.2 E
lectricity-conducting and electricityresponsive membranes
Electricity-conducting and electricity-responsive membranes (ERMs) are of interest as electrical potentials and
fields can be easily and quickly applied to the membrane
surface, making their use as drop-in replacements to
existing membrane modules a plausible prospect. ERMs
are defined as membranes in which surface properties
(i.e. surface charge and potential, hydrophobicity, roughness, and porosity) and mass transfer to and from the
membrane (i.e. electroosmosis, electrostatic attraction/
repulsion) can be modified using an external electrical
field or potential. Electrically conducting membranes
have been used for several application such as sensors,
electronic devices, and biomimetic devices (Meng and Hu
2010, Otero etal. 2012, Ates 2013, Guo etal. 2013). When
using membranes based on polymers for water treatment,
the electrically conducting polymers must be stable under
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2 Fouling mitigation
Fouling is the main reason for permeate flux decline and
increased energy consumption in membrane systems
(Goosen et al. 2005). Multiple examples of the use of
ERMs for fouling prevention have been published in the
last 5years, with mechanisms such as electrostatic repulsion, hydrogen peroxide (HP) production, electrochemical oxidation, morphological changes to the surface, and
piezoelectric vibrations. In the following sections, we
describe recent efforts in fouling mitigation using ERMs
by subdividing these efforts based on their antifouling
mechanism.
B 24
22
Pressure (psi)
Cross flow
Membrane surface
Permeate flow
20
1.5
-3.412 V
-1.519 V
-0.1 V
1.0
Force (nN)
Counter electrode
Electro force
18
16
0.5
0.0
14
12
0
20
40
60
Time (min)
80
100
-0.5
15
10
Distances (nm)
20
Figure 1:(A) Electrofiltration with conducive membrane/thin film setup. (B) Fouling of 5 g/l AA on PS-35 and PVA-CNT membranes. (C)
Overall force acting on an AA particle in a DIW solution containing 5 g/l AA at various distances from the surface and applied potentials at
ionic strength of 25.36 mm. (Reproduced from Dudchenko etal., Copyright 2014, with permission from Elsevier.)
Figure 2:(A) SEM micrographs of cross sections of a PVDF membranes before electrical poling and after poling at different magnifications
(the electrical field direction was the same and is shown in the diagram). (B) Effect of cross flow on normalized flux of a piezoelectric membrane excited by a 10-V AC signal at 500 Hz, an unexcited poled membrane, and an unpoled membrane after 35min filtration of a solution of
1 g/l PEG at 50 kPa. (Reproduced from Darestani etal., Copyright 2013, with permission from Elsevier.)
2.4 B
iological fouling and pathogen
inactivation
Biofouling is defined as the undesirable accumulation
of bacterial communities at the interface of the solid
Figure 3:(A) SEM image of surface of PA-CNT RO membrane. (B) (a) Electrically conducting RO membrane surface area after the application
of 2.5 V; the white area, corresponding to areas still covered by CaCO3 is greatly reduced. (b) Membrane area fully covered by CaCO3 scale. (c)
SEM of membrane surface after the application of 2.5 V displaying few CaCO3 crystals. (d) Thick CaCO3 deposits on fouled membrane surface
(no voltage applied); (C) As the applied surface potential increases, the region near the membrane where only SO42- ions exist expands out
into the solution, which pushes the nucleation zone away from the membrane surface. (Reproduced from Duan etal., Copyright 2014, with
permission from the Royal Society of Chemistry publishing.)
(i.e.membrane) and water phase. Fouling occurs by deposition, attachment and growth of bacterial communities
on the membranes (Guo etal. 2012). Although biofouling
is usually referred to in regard to bacteria, it is not limited
to it and could also develop from the deposition of yeast
and marine organisms (Callow and Callow 2002, Libana
etal. 2015).
de Lannoy etal. (2013) prepared a CNT-PA (polyamide)
composite material through an interfacial polymerization process that covalently bound the CNTs to the (PA)
through ester bonds. The membrane exhibited high electrical conductivity (~400 S/m), good monovalent ion
rejection (>95%), and water permeability compared with
commercial NF membranes. The authors demonstrated
that the application of an alternating block current (1.5 V)
to the surface of an electrically conducting NF membrane
prevented the formation of microbial biofilms (Figure4A).
Biofouling mitigation experiments were conducted using a
feed flow containing 10% Luria broth and high concentrations (108 CFU/ml) of Pseudomonas aeruginosa bacteria.
Biofilm-induced nonreversible flux decline was observed
in all control experiments. By contrast, when a potential
was applied to the surface, flux was fully recoverable following a short rinse with the feed solution and no added
cleaning agents (Figure 4B).
Singh et al. (2015) prepared a CNT/PVDF composite
membrane by using vacuum filtration, where the deposition of CNTs on a PVDF substrate was followed by a curing
treatment at temperatures higher than the melting point
of PVDF. These composite membranes had an electric conductivity of 0.41 S/m and functioned as MF membranes
(pore size ranging from 15 to 415 nm). Biofouling mitigation was evaluated in a dead end filtration cell using yeast
as a model biofouling agent while the membrane was used
B
Normalized flux
2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0
50
Time (h)
100
150
Figure 4:(A) TEM image of the composite PA-CNT membrane. Three layers are evident: the polyether sulfone support, the deposited CNT
layer, and the PA-CNT composite layer. (B) Control experiments without applied voltage and with highly resistive membranes with applied
voltage suffered from irrecoverable biofouling. CNT membranes, with applied voltage, demonstrated much longer resistance to flux decline
and flux was completely recoverable with 1min of cross-flow flushing. Red circles represent membrane flushing points. (Reproduced from
de Lannoy etal., Copyright 2013, with permission from American Chemical Society.)
7
6
B
No viruses in effluent (filtrate)
5
4
3
2
1
0
0V
2V
Applied potential
3V
0s
10 s
30 s
100
Loss of viability (%)
drying at ~90C. The unique properties of the polyurethane sponge are due to the conductive CNTs leading to a
low electrical resistance of 1 /cm and from the presence
of AgNWs, which produce a large number of nanoscale
sharp tips distributed on the sponges surface. The
pore size of the sponge was characterized as very large
(~500m). The ability of the sponge filter to remove bacteria and viruses was evaluated under flowing conditions
(15,000 LMH) by applying an external voltage (020V) to
two parallel sponge electrodes contained inside an in-line
filter holder. Disinfection performance was evaluated
using four different model bacteria representing Gramnegative and Gram-positive species. Results show that
bacterial inactivation was enhanced with increasing external voltage for all four bacteria, indicating that a stronger
electric potential results in more efficient disinfection. For
voltages above 10 V, all four bacterial species were inactivated at over 6 log (99.9999%) removal, corresponding
to no culturable bacteria detected in the effluent, with a
retention time of only 1 s. In addition, virus inactivation
was evaluated using a model virus (MS2) and a bacteriophage (F+), which is related to enteric pathogenic viruses
in groundwater and raw wastewater. Results demonstrate
that inactivation increased with greater external voltage,
with 99.4% inactivation at a voltage of 20 V. The bacterial
disinfection mechanism was claimed to be based on electroporation of the cell membrane. Reversible electroporation was detected when lower potentials were applied. The
disinfection process was enhanced by the release silver
ions from the AgNWs, which could enter the bacterial
cell after the cell membrane was damaged, reacting with
inner cellular components to disrupt cell function. Lower
applied potential demonstrated lower removal rates, with
5V being the lowest voltage where removal was observed.
Direct
Indirect
80
Ox
60
Ox
40
20
0
2
Potential (V)
e-
e-
Figure 5:(A) Electrochemical MS2 removal vs. potential, Log MS2 removal as a function of applied potential during filtration. Influent was
10ml of 10 mm NaCl (pH 5.7) and 106 viruses ml-1. (B) Electrochemical loss of Escherichia coli viability versus potential and time. E. coli
suspension (107 cells, [NaCl]=10 mm, pH 5.7). (C) Electrolytic inactivation mechanisms. (Left) Depiction of direct electrochemical oxidation
of bacteria adhered to CNT surface and of indirect (right) electrochemical production of aqueous oxidant that subsequently inactivates the
bacteria in solution. (Reproduced from Vecitis etal., Copyright 2011, with permission from American Chemical Society.)
It should be noted that in addition to direct and indirect oxidation, applying anodic potential on bacteria
colonies and biofilms has been shown to induce oxidative
stress because of the presence of hydroxyl radicals and
HP. Although these could lead to bacterial detachment,
damage to the cell membrane and increased susceptibility to antibiotics (Baatout etal. 2006, Barraud etal. 2006,
Narendra and Ramesh 2012, Munna etal. 2013), research
shows that they also function as a signaling molecule (p
et al. 2012) and could increase genetic variants, eventually increasing the diversity of bacteria, which may lead to
adaptability in biofilm communities and a more sustainable biofilm (Boles and Singh 2008).
3 Permselectivity
In conventional polymeric membranes, selectivity is
mainly a function of pore sizes, although modified
membranes (with nanoparticles or zwitterionic groups
attached to their surface) have shown tunable permselectivity. However, permselectivity is limited in terms
of control, which relies on changes in the surrounding
pH (Chan etal. 2014, Geise etal. 2014, Ji etal. 2016). By
contrast, ERMs can be tailored to optimize rejection and
to control ion selectivity (permselectivity) by applying
electrical potential and electrostatically charging the
membrane surface (Kuo et al. 2001). Under these conditions, counter ions are attracted to the membrane surface,
whereas co-ions are rejected.
Weidlich and Mangold (2011) coated PVDF and polyethersulfone membranes with an electrically conductive
polypyrrole (PPy) film (Figure 6A) using a diffusion-limited
oxidation process. Membrane properties (film thickness
and permeate flux) were correlated to the polymerization time and the counter ions incorporated into the PPy
coating during polymerization. Permselectivity experiments were conducted by applying a potential (800 mV)
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Figure 6:(A) SEM cross section of a PPy coated MF membrane (polyethersulfone, 0.22 m) after 15min polymerization. (B) Ca2+ concentration in permeate passed a MF membrane (PVDF, 0.22 m) coated with PPy with PSS counter ions in dependence on cathodic (-800mV or
-0.7mA cm-2) or anodic (+800mV or +0.8mA cm-2) potentiostatic or galvanostatic polarization. (Reproduced from Weidlich etal., Copyright
2011, with permission from Elsevier.)
3.1 P
ermselectivity in conventional
membranes vs. ERMs
Permselectivity is considered when charged membranes
allow specific species to be transported while restricting
the passage of other species. For water treatment aspects,
ion exchange membranes and charged NF membranes are
considered as permselective as they have fixed charges
on the membrane surface (Xu 2005, Nagarale etal. 2006,
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4 E
lectrochemical reactions
coupled with membrane filtration
Electro-oxidation and electro-Fenton (E-Fenton) are processes that can be used for the oxidation and degradation
of aqueous contaminants (e.g. pesticides, pharmaceuticals, and personal care products). Using ERMs allows
for these degradation reactions to occur during filtration,
with the benefit of a large membrane active surface area
and high mass transport rates (Gao etal. 2015). E-Fenton
reactions are initiated by the in situ electrochemical production of HP via the cathodic reduction of O2, followed
by the reaction of HP with iron (Fe2+) to generate hydroxyl
radicals (Ayadi et al. 2013, Zhao et al. 2013a, Gao et al.
2015). There are several types of E-Fenton reactions, where
the most promising include ferric ion reduction to ferrous
ion at the cathode and the production of hydroxyl radicals
in an electrolytic process. However, ferric ion regeneration
is slow even at an optimal current density, and the production of HP is slow because oxygen has low solubility in
water (Babuponnusami and Muthukumar 2012). Electrooxidation (Vecitis etal. 2011a,b, Liu etal. 2014) is based on
an anodic reaction on the membrane surface and can be
attributed to two mechanisms: (1) direct oxidation driven
by contact with the conductive membrane and (2) indirect
oxidation by anodic production of an aqueous oxidant
(e.g. chlorine and hydroxyl radicals).
4.1 Electro-Fenton
Gao et al. (2015) used a multiwall CNT membrane stack
for sequential electro-Fenton reactions. In the CNT membrane stack (overall thickness ~200 m), the feed initially
goes through a cathodic CNT network that reduces O2 to
HP. Next, the feed passes through a CNT-COOFe2+ cathode,
used to chemically reduce HP to hydroxyl radicals and
to regenerate Fe2+. In the final stage, the feed is passed
through a CNT filter anode for oxidation of any remaining intermediates. Results indicate high organic removal
at low cell potentials (<3.0 V) because of the thickness of
the stack, which allowed for a long contact time, and convective mass transport. In addition, as Fe was bound to
the electrode, the E-Fenton reaction was able to operate at
neutral pH and recycle the Fe2+ by in situ electrogeneration.
Zhao et al. (2013a) modified a polyester membrane
by impregnating it with graphene and by coating it with
polypyrrole using a vapor phase polymerization method.
After modification, the composite membrane had an electrical resistance of 0.7 k/cm. The membrane was used as
a cathode (-1 V DC), and a stainless iron mesh was used
as an anode. The modified membrane was evaluated for
the removal of methylene blue (MB) as a model compound
through an E-Fenton reaction under membrane filtration conditions. The feed solution contained 0.2mmolL-1
ferrous ion, 0.05 mol L-1 Na2SO4 as electrolyte, and
5 mg ml-1 MB. The membrane proved to be stable under
multiple cycles, with a constant removal rate of approximately 90%. In addition, the applied potential and the pH
level were determined to play key roles in the E-Fenton
reactions, with potential increases leading to enhanced
H2O2 generation,, and the pH affecting the stability of Fe2+
ions, which were found to be stable between a pH of 2.5
and 4. Higher pH values increase iron precipitation in
the Fe(OH)3 form. When applying a potential of -1 V to the
membrane with a flux of ~100 LMH at pH 4, 95% of MB
was removed after 90 min.
Figure 7:(A) SEM of the CNT filter. (a) Aerial image of the CNT filter with an average pore size of 115 nm. (b) Cross-sectional image of the CNT
filter with an average height of 41 m. (B) Mechanisms of interaction for dyes with CNT filter. (C) Electrochemical desorption and/or oxidation of adsorbed methyl orange dye as a function of applied potential. Dye adsorption was completed in the absence of applied potential.
Negative time points are the time prior to application of potential at t=0 noted by the vertical dashed line-adsorbed methyl orange oxidation
at potentials of 1 V (black squares), 2 V (red circles), and 3 V (blue triangles). (Reproduced from Vecitis etal., Copyright 2011, with permission
from American Chemical Society.)
4.3 E
lectrochemical reactions in ERM vs.
advanced oxidation processes
Because electrochemical reactions coupled with ERM
are not applicable with conventional membranes, a comparison between ERM and common advanced oxidation
process (AOP) is discussed in terms of energy consumption. For the removal of a model compound (MB), it was
demonstrated by Legrini etal. (1993) that using a photocatalytic treatment requires high energy consumptions
and a long contact time (i.e. 40 kW m-3 and a typical
contact time of 3060 min) (Lachheb et al. 2002). A
similar electrochemical process using ERM has significantly lower energy requirement and lower contact time
(i.e. 0.16kWm-3 and a typical contact time <1.2 s) (Vecitis
etal. 2011a,b).
5 Future directions
Three promising future applications of ERM are presented
below. The first allows control of the membranes flux by
changing the pore size of a metallic grid coated by a conducting polymer (Jeon etal. 2011, Abelow etal. 2014). This
5.2 Electrowettability
Teng etal. (2015) developed a conductive polymer porous
film with tunable wettability. The film was fabricated from
6 Conclusions
Membrane separation processes have been part of the
water treatment industry for the last half century, with
major improvements in separation, fouling prevention,
and transport properties achieved over the last decade.
Although commercial membranes are efficient, fouling
of the membrane is still an inevitable issue. Polymeric
and inorganic ERMs show promising abilities for membrane separation processes. The ability to change the
membranes properties (surface charge, flux, wettability, and redox potential) and to prevent fouling through
electrostatic repulsion and electrochemical reactions
makes them ideal for wastewater treatment and water
desalination. Although a significant part of the literature deals with fouling prevention, new and advanced
treatments such as electro-oxidation and E-Fenton show
encouraging results in the removal of organic compounds
and pollutants, which are not fully removed by commercial membranes (e.g. some pharmaceuticals and small
uncharged molecules). ERM separation is still facing
some challenges regarding implementation, as each ERM
module must include a counter electrode, which increases
the cost of the initial setup and also calls for engineering
solutions in terms of a different flow cell structure. For
example, ERMs have been demonstrated to be efficient
in a tubular and flat sheet setup, but more complicated
spiral-wound ERM modules have not been fabricated yet.
In addition, at anodic conditions ceramic membranes
have been demonstrated to be stable, whereas polymeric
membranes suffer from stability limitations. Therefore,
additional research is needed in this field to allow cheap
and stable polymeric ERMs.
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