Desalination 517 (2021) 115183

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Emerging desalination technologies: Current status, challenges and

future trends
Farah Ejaz Ahmed, Abdullah Khalil, Nidal Hilal *
NYUAD Water Research Center, New York University Abu Dhabi, Abu Dhabi, P.O. Box 129188, United Arab Emirates

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Near-commercialization and early stage

emerging desalination technologies
reviewed.
• Membrane distillation is promising for
mineral recovery from brine solutions.
• Draw solution recovery remains a
deterrent to low energy desalination
using forward osmosis.
• Battery-based desalination linked to
revival of electrochemical technologies
for brackish water and seawater
desalination.
• More pilot-scale studies needed to in­
crease technology readiness of emerging
processes.

A R T I C L E I N F O A B S T R A C T

Keywords: Emerging technologies present many new possibilities for diversifying the desalination industry, which is
Emerging technologies currently dominated by thermal desalination, and reverse osmosis. In this review, we highlight recent de­
Membrane distillation velopments in emerging desalination technologies, focusing on those nearing commercialization i.e. forward
Forward osmosis
osmosis and membrane distillation, as well as electrochemical processes that hold potential for technological
Electrochemical desalination
Monitoring
maturity and upscaling. Literature shows that emerging desalination technologies have benefited greatly from
Fouling control advances in nanomaterials. However, a membrane-based approach alone will not realize commercialization of
Hybrid desalination forward osmosis or membrane distillation. In the case of forward osmosis, appropriate selection of draw solute as

Abbreviations: MED, multi-effect desalination; MSF, multi-stage flash; RO, reverse osmosis; ZLD, zero liquid discharge; FO, forward osmosis; PRO, pressure
retarded osmosis; MD, membrane distillation; CDI, capacitive deionization; ED, electrodialysis; SWRO, seawater reverse osmosis; EDR, electrodialysis reversal; FD,
freeze desalination; DS, draw solution; NF, nanofiltration; TFC, thin film composite; ICP, internal concentration polarization; TFNC, thin film nanocomposite; PA,
polyamide; TMC, trimesoyl chloride; MOF, metal-organic framework; PSU, polysulfone; PAN, polyacrylonitrile; GOQD, graphene oxide quantum dots; CNTs, carbon
nanotubes; Js, reverse salt flux; Jw, water flux; CTA, cellulose triacetate; GO, graphene oxide; PES, polyethersulfone; HNT, halloysite nanotube; NCC, nanocrystalline
cellulose; NIPS, nonsolvent induced phase separation; PC, polycarbonate; DOTM, direct observation over the membrane; UTDR, ultrasonic time domain reflec­
tometry; OCT, optical coherence tomography; TDS, total dissolved salinity; DCMD, direct contact membrane distillation; VMD, vacuum membrane distillation;
SGMD, sweeping gas membrane distillation; AGMD, air gap membrane distillation; PTFE, polytetrafluoroethylene; PP, polypropylene; PVDF, polyvinylidene fluoride;
SDS, sodium dodecyl sulfate; PEG, polyethylene glycol; BDD, boron doped diamond; EO, electrochemical oxidation; AEM, anion exchange membranes; IEM, ion
exchange membranes; CuHCF, hexacyanoferrate; PB, Prussian blue; PBA, Prussian blue analogues; NaNiHCF, nickel hexacyanoferrate; NaFeHCF, sodium iron HCF;
TRL, technology readiness level; FDFO, fertilizer drawn forward osmosis; TrOC, trace organic compound.
* Corresponding author.
E-mail address: nidal.hilal@nyu.edu (N. Hilal).

https://doi.org/10.1016/j.desal.2021.115183
Received 3 May 2021; Received in revised form 1 June 2021; Accepted 1 June 2021
Available online 27 July 2021
0011-9164/© 2021 Elsevier B.V. All rights reserved.
F.E. Ahmed et al. Desalination 517 (2021) 115183

well as low-cost recovery of the draw solution towards low energy consumption will be important in full-scale
commercialization. In membrane distillation, use of low-grade heat as well as hybrid systems driven by
renewable energy sources are likely to facilitate growth. We also review advances in smart process monitoring
and control through innovative in situ methods that can further lower operational costs associated with manual
sampling and frequent membrane replacement, particularly in membrane distillation. Furthermore, break­
throughs in desalination batteries to remove salt ions using high capacity battery materials may lead to the
revival of electrochemical processes for seawater desalination as well as niche desalination applications. Future
work should be geared towards optimization of system design and economic assessment of upscaling.

1. Introduction had a capacity of 60 m3/day [18]. Many large-scale thermal distillation

Water scarcity is a raging global issue that is expected to worsen in
coming years. Today, over two billion people lack access to safe and
clean water [1]. Population growth and subsequent demand for agri­
culture have doubled human water consumption over the last few de­
cades [2]. Rapid urban growth has also contributed to water stress
through increasing demand for water in urban areas [3] and deterio­
ration of water quality due to discharge of industrial wastes [4]. Human-
induced climate change is also linked to changes in water availability
and increased risk of drought [5–9]. These factors have resulted in
growing stress on the world’s water reserves, which in turn affects global
access to health and sanitation as problems related to sanitation
concurrently rise.
Less than three percent of the world’s water exists as freshwater
suitable for direct use, and even less is available and accessible to us.
Most of the world’s water is present as seawater and is unsuitable for
consumption due to its high salinity. Other sources of water such as
groundwater and produced water from oil and gas extraction are also
saline, containing varying types and concentration of salt ions. Saline
water must be converted into freshwater using desalination
technologies.
The process of desalination, i.e. removal of salts and other minerals
from feedwater, has long been used to extract freshwater from seawater
and other saline sources, allowing humankind to benefit from a poten­
tially abundant supply of water. Although water-scarce regions such as
the Middle East and North Africa have traditionally been key players in
seawater desalination, climate change and unprecedented water stress
have pushed coastal communities worldwide to employ desalination as a
means of obtaining potable water and diversifying their water supply
[10]. Desalination technologies are thus critical for the sustainable
development of humankind [11]. Several countries have adopted water
management initiatives that involve desalination projects. This has led
to a continuously upward trend in global desalination capacity, with the
global desalination equipment market size projected to reach USD 32
billion by 2025 [12]. Expansion of water-intensive industries such as
chemical manufacturing and oil and gas have also contributed to the
rapid growth of desalination in recent years. Semiconductor
manufacturing, which is central to the electronics industry, also requires
large amounts of ultrapure water [13].
Today, most desalination processes fall into one of two categories:
thermal desalination or membrane processes. Thermal desalination in
its simplest form consists of evaporating salty water and then
condensing the resulting steam to obtain freshwater. This form of
desalination has been used for centuries to obtain freshwater. In as early
as the 4th century BC, Aristotle described a thermal desalination tech­
nique involving evaporation and condensation of saltwater [14].
Ancient Egyptians also used solar thermal systems to produce potable
water [15,16]. During the age of modern colonialism, distillation
became a commonly used technique to produce potable water on ships.
However, it was not until the advent of the steam engine during the
Industrial Revolution when improvements in evaporators and an
increased need for freshwater supplies in remote areas led to swift de­
velopments in distillation apparatus [17]. The very first land-based
desalination plant was installed in 1928 in Netherlands Antilles and
plants have been installed in the Middle East, particularly Saudi Arabia,
since the 1930s following the discovery of oil in the kingdom [19]. These
are mainly based on multi-effect distillation (MED) or multi-stage flash
(MSF) processes.
Reverse osmosis (RO) desalination on the other hand only became a
commercially viable option with the discovery of suitable polymer films
in the 1960s [20]. With the capability to desalinate water at a lower
energy consumption compared to then traditional phase-change desa­
lination processes, the commercialization of membrane-based RO
desalination presented a breakthrough in desalination. Some of the
challenges that membranes helped overcome included space in­
efficiency, scaling of heat exchanger surfaces and high energy con­
sumption. The desalination industry witnessed a boom over the next few
decades; today, the global installed desalination capacity stands at 97.2
million m3/day [10]. RO currently makes up >60% of the world’s
installed desalination capacity and represents the fastest growing
segment of the seawater desalination market [21]. Compared to thermal
desalination, membrane-based desalination technologies boast low en­
ergy and ease of operation. The former has been further amplified by
advances in the development of membrane materials, energy recovery
devices and high efficiency pumps [22].
As the demand for desalination continues to grow, a few factors have
forced researchers to explore alternative technologies. First, the overall
energy consumption of RO plants remains high. Although development
of energy-efficient pumps, energy recovery devices and high flux
membrane materials have significantly reduced energy consumption of
seawater RO (SWRO) from 20 kWh/m3 in the 1970s [23] to 2-5 kWh/m3
today [24,25], the increasing energy requirement with increasing feed
salinity still makes it challenging to treat feed solutions with high
salinity from an energy standpoint. This includes hypersaline reject
brine from desalination, the safe disposal of which is a budding envi­
ronmental concern. Treatment of brine has received significant interest
with increasing volume of desalination byproducts and stringent regu­
lations on their disposal. Hypersaline feed conditions are also present in
regions with high evaporation rates, such as the Arabian Gulf [26]. In
fact, the high salinity and harsh feed conditions that necessitate rigorous
pretreatment methods are both contributing factors in the slow transi­
tion from thermal technologies to reverse osmosis in the region. Another
incentive to diversify desalination technologies is the presence of other
applications where mature technologies would make little economic or
practical sense. Examples include zero liquid discharge (ZLD) [27],
brine management [28], saline wastewater treatment [29], produced
water treatment [30], food and dairy industry [31], pharmaceuticals
and electronics [32]. In recent years, emerging desalination technolo­
gies have shown remarkable promise in these areas. Researchers have
turned to developing processes with low energy requirements to over­
come existing challenges in reverse osmosis, MED and MSF technolo­
gies. Emerging desalination technologies have the potential to compete
with conventional technologies for seawater desalination, or to
outperform these technologies in niche areas; however, their transition
to full-scale employment depends on further scientific advances to
achieve threshold performance and energy efficiency.
One way to lower the energy consumption of desalination processes
is to exploit the osmotic energy of saline solutions, to reduce the net

2
F.E. Ahmed et al.
energy consumption in RO. The most prominent example of this type of
osmotically driven desalination is forward osmosis (FO). Research in FO
has seen a massive surge since the beginning of the 21st century, and
although many have touted its benefits over RO desalination, the
commercialization of FO still faces many hurdles. Progress in FO has also
driven the development of other osmotically driven processes such as
pressure retarded osmosis (PRO), osmotically enhanced RO, etc., which
currently remain at the lab scale.
Membrane distillation (MD) at present is also considered a promising
emerging desalination technology. MD is a thermally driven membrane
process in which a vapor pressure difference between the two sides of a
membrane causes vapor to penetrate through its pores. Compared to
traditional thermal desalination methods, MD has lower heating re­
quirements and its modular design makes it simple and compact. Despite
decades of promising research into novel membrane materials and sys­
tem design, both FO and MD remain largely limited to pilot scale fa­
cilities. Efforts are underway for investigating these technologies as a
competitive alternative to RO as well as for other applications such as
treatment of reject brine. To date, numerous publications have reviewed
the progress, material development, future challenges and applications
of both forward osmosis [33–39] and membrane distillation [40–50].
Hence, only the latest developments in membrane material fabrication
as well as the technological status of these technologies are reviewed
here.
In recent years, we have also witnessed a revival of electrochemical
desalination processes, specifically advancements in capacitive deion­
ization (CDI) due to the development of high capacity carbon and
non‑carbon electrode materials.
In the past, researchers have reviewed progress in several aspects of
desalination processes to guide energy-efficient desalination. Due to
growing attention on replacing fossil fuel energy with renewable energy,
some have focused on recent advances in integrating renewable energy
with desalination processes [51,52]. Subramani et al. compared various
emerging desalination technologies, focusing on the treatment of in­
dustrial and municipal wastewaters [53]. Goh et al. also reviewed trends
in membrane materials and processes for desalination, focusing on FO,
PRO, MD and CDI [54]. Status of the same technologies were later
assessed by Skuse et al. [55] who highlighted opportunities and current
challenges and compared their level of readiness with SWRO. The
environmental impact of emerging technologies, namely forward
osmosis (FO), membrane distillation (MD) and electrodialysis/electro­
dialysis reversal (ED/EDR) against SWRO was recently evaluated by
ElSaid et al. [56]. Although other technologies such as freeze desalina­
tion (FD), adsorption-absorption are also applied to desalination, we
focus this review on three key emerging desalination groups: FO, MD
and electrochemical desalination methods.
With ever-growing developments, in materials and processes, espe­
cially in the last five years, there is a need to review trends and identify
research gaps in emerging desalination technologies towards full-scale
commercialization. In this review, we focus on recent research, tech­
nological challenges and shortcomings of emergent technologies for
desalination, which includes those that are nearing commercialization,
as well as new ideas in electrochemical desalination. By highlighting
recent advances in materials and system design, we explore factors that
have prevented the full-scale implementation of FO and MD, and discuss
material progress in these technologies that could pave the way for
technological maturity in the near future. We also shed light on ad­
vances in monitoring and control, as well as relatively new concepts at
the intersection of desalination and electrochemical batteries that go
beyond existing ED and CDI systems.
2. Emerging desalination technologies
2.1. Forward osmosis
Osmotically driven processes rely on the natural osmosis
3
Desalination 517 (2021) 115183
phenomenon by which a solvent, in this case water, moves from low
solute concentration to high solute concentration. In forward osmosis, a
concentrated draw solution on the permeate side is used to draw in
water from the feed side of the membrane into the draw solution (DS).
Depending on the membrane orientation, there are two operational
modes in FO systems: one where the active layer is facing the feed so­
lution (FO mode) and one where the active layer is facing the draw
solution (PRO mode). As it is a naturally occurring phenomenon, the
energy consumption for forward osmosis is low compared to pressure-
driven processes, and FO membranes also have a lower tendency to
foul [57]. However, FO desalination is a two-step process in which, the
osmosis step must be followed by recovery of the draw solution. Desa­
lination via FO relies not only on osmotic transport of water molecules
through an FO membrane using a concentrated draw solution, but also
subsequent recovery of the draw solution. The contribution of the re­
covery step to overall energy consumption, although frequently over­
looked, can be significant depending on the process applied, choice of
draw solute, etc. Conflicting results have been reported on the energy
consumption of FO combined with nanofiltration (NF) or RO for draw
solution recovery as compared to conventional RO: some studies suggest
that the FO-NF/RO system consumes more energy, while others have
found the reverse to be true [58]. This aspect is further discussed in
Section 4.1.
A recent bibliometric analysis conducted by Ang et al. [36] showed
that the number of articles on FO have increased rapidly since 2009 and
have been steady at about 250 annual publications from 2016 and 2018.
Developments in FO membrane materials, mainly in USA, China,
Singapore, Australia and South Korea have driven this surge. Fig. 1
shows growing number of research publications focusing on forward
osmosis between 2001 and 2020. Recent trends in FO desalination
research target functional membrane materials, appropriate choice of
DS and suitable DS recovery method to reduce the energy consumption
and make FO a competitive process for desalination. Here, we review
advances mainly in membrane materials for forward osmosis and ob­
stacles to large-scale industrial use of the technology.
2.1.1. Membrane materials
The quest for high flux, high salt rejection membranes has driven FO
membrane research. FO membranes should also have high rejection for
the draw solute, to prevent reverse salt flux, and low propensity to foul.
When using thin film composite (TFC) membranes, it is important to
optimize the design of each layer: the active layer should be dense and
thin to support high flux and high solute rejection. The role of the
support layer for FO is very different from that for RO; in fact, TFC-RO
membranes could pose a disadvantage when used for FO due to the
support layer. For this reason, there has been a strong focus on support
layer design for FO desalination. Other factors to consider are hydro­
philicity and mechanical stability, both of which are desirable. FO
membrane research aims to tackle some of the challenges associated
with existing FO membranes.
In early FO studies, TFC-RO membranes were employed, the support
layer of which was designed to sustain high hydraulic pressures. These
relatively thick support layers hindered FO performance by acting as a
diffusive boundary layer and thus reducing the osmotic pressure
gradient across the active layer [59]. This phenomenon, known as in­
ternal concentration polarization (ICP), significantly reduces the driving
force for mass transfer, limiting water flux and reducing FO performance
[60]. The degree of ICP is determined by the structural parameter S of
the support, related to support layer geometry, in particular thickness,
tortuosity and porosity. Careful design of the substrate is considered an
effective approach to mitigate ICP and reduction of S [61,62]. A mem­
brane suitable for forward osmosis should have a water permeability of
at least 1 L m− 2 h− 1 bar− 1, high rejection towards both feed and draw
solute and low S to minimize ICP [63]. Due to the challenges of over­
coming ICP and enhancing membrane performance, exploration of
fabrication techniques and modification strategies for the support layer
F.E. Ahmed et al.
Fig. 1. Number of publications on ‘forward osmosis’ from 2000 to 2020 (Scopus).
in particular has been an integral part of recent FO membrane research.
This is evidenced by recently published reviews focusing on the support
layer [64–67]. Here, we consider some of the latest advances in modi­
fying active and support layers for enhanced FO performance.
2.1.1.1. Modification of active layer with nanomaterials. TFC membranes
most commonly use polyamide (PA) as the active layer on a porous
substrate. A thin PA film is formed via interfacial polymerization be­
tween m-phenylenediamine (MPD) and trimesoyl chloride (TMC)
monomers [68]. Incorporation of nanomaterials as nanofillers into the
active or support layer have given rise to thin film nanocomposite films
(TFNC) for separation processes. This was first realized in 2007 for RO
processes with nano-zeolite was incorporated into the PA layer to ach­
ieve a near doubling of the pure water flux at the same salt rejection
[69]. A few years later in 2012, the first study involving TFNC for FO
was published [70,71]. The same group went on to incorporate super-
hydrophilic zirconium (IV)-carboxylate metal-organic framework
(MOF) UiO-66 nanoparticles in the PA layer using a polysulfone (PSU)
support. At 0.1 wt% nanoparticle loading, they achieved a 52% increase
in water permeability while retaining salt rejection levels at 95% [72].
Fig. 2 shows the FO performance with respect to water flux and reverse
salt flux for membranes with varying UiO-66 loading. Another group has
also studied the effect of incorporating nano-sized silver-based MOFs to
PA membranes for FO, with improved flux and resistance to biofouling
[73,74].
Recently Yang et al. [75] investigated a TFC membrane with a triple-
layer structure applying carbon nanotubes (CNTs) as an interlayer be­
tween the PA active layer and electrospun polyacrylonitrile (PAN)
Fig. 2. FO performance of TFNC membranes with varying nanoparticle loading under (a) PRO mode, and (b) under FO mode, using 1 M NaCl as draw solution and DI
water as feed. U1, U2, U3, U4 and U5 refer to UiO-66 loading of 0, 0.05, 0.1, 0.15 and 0.2% respectively. Reprinted with permission from [72]. Copyright (2017)
American Chemical Society.
4
Desalination 517 (2021) 115183
support. The interlayer serves to reduce the pore size of the support and
improve formation of the active layer. Water flux increased by 84%
whereas reverse salt flux dropped by 76% when compared to the un­
modified TFC membrane. Building on this work, Wang et al. [76]
applied CNTs as the interlayer and incorporated silver decorated gra­
phene oxide quantum dots (GOQD) [77] into the PA layer. They found
that the triple-layered TFNC membrane resulted in further enhanced
flux and reduced specific reverse salt flux using 1 M NaCl as draw so­
lution. In particular Js/Jw, or the ratio of reverse salt flux to water flux is
an indicator of FO selectivity: the lower this ratio, the higher the
selectivity. TFC-GOQD/Ag1 exhibited the lowest Js/Jw, which the au­
thors attributed to the synergistic effect of the CNT interlayer and the
nanofiller. By reducing the pore size of the support, the CNT interlayer
helped achieve an ultrathin PA layer with lower mass transfer resistance.
The GOQD/Ag nanofillers provided additional nanochannels to support
water transport through the membrane [76]. However when the nano­
filler loading exceeded 1 mg mL− 1, Js/Jw increased possibly due to ag­
gregation of the nanofiller in the active layer (Fig. 3). In another study,
Xu et al. were able to obtain a dense, flat PA layer by cross-linking
GOQDs containing amino groups (NH2-GOQDs) with triacyl chloride
and PA oligomers [78] with stable long-term FO selectivity.
Other groups have also explored graphene-based nanomaterials in
TFC-FO membranes [79–87]. Balapanuru et al. [88] fabricated a free-
standing partially oxidized few-layer graphene membrane >1 m2.
Their results showed that the partially oxidized membrane exhibited a
seven fold enhancement of water flux compared to a commercial cel­
lulose triacetate (CTA) membrane. The FO performance of the partially
oxidized membrane was superior to that of heavily oxidized graphene
F.E. Ahmed et al.
Fig. 3. Js/Jw value of the FO membranes under PRO mode using 1 M NaCl as
DS and DI water as FS with increasing GOQD/Ag concentration [76].
oxide (GO) due to smaller interlayer distance [88]. Manawi et al.
recently pointed out that carbon nanomaterials based membranes have
only been used in lab-scale studies [89].
2.1.1.2. Modification of support layer. Hodadpour et al. [90] studied the
effect of incorporating different amounts of charcoal-based carbon
nanomaterial into the polyethersulfone (PES) support on membrane
properties and FO performance. They found that the carbon nano­
material, synthesized via acid treatment of charcoal, reduces S and
therefore reduces the negative effects of ICP, with water flux approxi­
mately 3 times higher in the membrane modified with 0.5% carbon
nanomaterial than the neat membrane. Rezai-DashtArzhandi et al. have
recently modified an FO membrane with dual nanofiller, one in the
substrate and one in the active layer. They incorporated halloysite
nanotube (HNT) into the PSU substrate, and nanocrystalline cellulose
(NCC) within the PA thin film layer. They found that the incorporation
of hydrophilic NCC at just 0.1 wt/v% increased membrane flux by 140%
compared to the unmodified membrane [91].
Alternative fabrication techniques have also been investigated for
the FO TFC support layer. The last decade has seen the growth of elec­
trospinning in particular for various applications from drug delivery,
pharmaceuticals, textiles and water treatment. The high porosity,
interconnected structure make electrospun nanofibers suitable as a
support in TFC membranes. Song et al. were the first to fabricate a
nanofibrous support for FO membrane via electrospinning [92]. Since
then, electrospinning has extensively been used to fabricate the support
layer in TFC-FO membranes. This includes electrospinning pristine
polymers, modification of as-spun fibers by surface coating or blending
with hydrophilic polymers, modification of as-spun fibers by adding
inorganic nanoparticles and using electrospun nanofibers as nonwoven
substrate in TFC-FO membranes [93]. Progress in the fabrication of
electrospun nanofiber-supported TFC-FO membranes up until 2019 has
been reviewed by Obaid et al. [93] recently.
Han et al. [62] fabricated aligned PAN nanofibers via electrospinning
as a substrate with slit-pore structure by varying the drum rotation
speed. Due to large pore size and interconnected pore structure, the
membrane achieved a high water flux of 50.7 L m− 2 h− 1 in FO mode,
with DI water as feed and 1 M NaCl as DS, as well as ultralow reverse salt
flux.
The use of alternate materials for the support, away from the tradi­
tional phase inversion PES, has also been suggested. Alihemati et al. [94]
explored the feasibility of polycarbonate (PC) substrates prepared via
the Loeb-Sourirajan method for TFC-FO interfacial polymerization
polyamide (PA) membranes and compared their performance with PES
supported membranes. PC is hydrophilic with pores 172% larger than
5
Desalination 517 (2021) 115183
those in PES. However, the greater pore size did not translate into su­
perior FO performance, as shown in Fig. 4.
Table 2 shows materials and fabrication methods used recently in the
support layer of FO TFC membranes. The two most common fabrication
techniques for the support layer are nonsolvent induced phase separa­
tion (NIPS) and electrospinning. Both these methods are simple and
versatile, allowing the properties of the end membrane to be tuned via
control of polymer solution and operating conditions.
2.1.2. Draw solutes
The choice of draw solution is an important parameter in deter­
mining FO performance. The first requirement of the draw solution is
that it must have a high osmotic pressure, to allow osmotic flow of water
from the feed to the draw. To minimize the effects of concentration
polarization, the draw solute must ideally be soluble in water with low
viscosity in water to promote diffusion. Another important feature of the
draw solution is that it must be efficiently regenerated using low-cost
techniques to keep the overall energy consumption from the regenera­
tion step low. Ionic compounds with low molecular weight and high
solubility are a popular choice of draw solute, as can be seen in Table 3.
For a detailed review of draw solutes for FO, the reader is referred to
a recent review by Johnson et al. [103]. Additionally, suitable draw
recovery processes in hybrid with FO are discussed elsewhere [104].
2.1.3. Real time monitoring in FO
Monitoring water quality and plant productivity are important as­
pects of ensuring safe operation of any desalination system. Permeate
conductivity is regularly measured to ensure product water quality
meets required standards. Permeate conductivity can be measured at the
end of the process, but that does not enable identification of faulty
membranes. In many desalination plants, manual sampling from pipes is
taken from each membrane element until the fault is found, which is
time-consuming and cost-intensive [105]. Similarly, fouling and scaling
is also detected by monitoring flux and/or membrane autopsy. The first
is slow while the second can only take place once the membrane is
removed from the module. Much research has recently focused on non-
invasive and in situ monitoring techniques for membrane processes that
would support preventive maintenance and intelligent planning of
membrane replacement. In membrane distillation, these studies have
focused on monitoring wetting phenomena, monitoring development of
fouling during MD and appropriate control of fouling.
Several in-situ techniques have been applied to monitor fouling in FO
systems in real time. These include optical, magnetic and electrical
techniques. In the case of transparent membranes, direct observation
over the membrane (DOTM) have been proposed as a sensitive tool to
detect fouling [106,107].
Ultrasonic time domain reflectometry (UTDR) is a non-destructive
technique in which an ultrasound wave is transmitted through media,
Fig. 4. Water flux of polycarbonate (PC) support compared to PES for TFC PA
membranes [94].
F.E. Ahmed et al. Desalination 517 (2021) 115183

and reflected waves from interfaces, indicative of acoustic impedance, operation exist depending on heat transfer on the permeate side. These
are recorded [108]. UTDR has previously been applied to fouling are direct contact membrane distillation (DCMD), vacuum MD (VMD),
detection in microfiltration [109], reverse osmosis [110,111]. However, air gap membrane distillation (AGMD) and sweeping gas membrane
the loosely packed foulant layer in FO made it challenging to use UTDR distillatio (SGMD). The simplest of these is DCMD, in which the mem­
for fouling characterization in FO as the amplitude of the measured brane is directly in contact with the cold permeate. Although DCMD has
signal is proportional to the density of the layer. Lai et al. [112] were the the lowest energy efficiency, it is most commonly used in the lab because
first group to employ UTDR for characterization of fouling in FO. They of its simple design. The other modes aim to improve thermal energy
used UTDR to measure the thickness of the cake layer and observe pore efficiency and reduce heat loss through the membrane. On the other
clogging, using colloidal silica as the model foulant; they showed that hand, most pilot-scale plants for MD operate on VMD or AGMD. For a
UTDR is a better indicator of fouling than flux decline. detailed description of each mode, the reader is referred to [115].
Optical coherence tomography (OCT) is another real-time moni­ Table 5 summarizes key challenges in MD and recent approaches
toring tool which analyzes interference signals to detect structures and adopted by researchers to combat each of these.
foulant layers during dynamic processes. Gao et al. [113] were the first In the following subsections, we discuss recent advances in mem­
to demonstrate fouling detection in filtration processes using OCT. Liu brane materials, process control as well as the technological status of
et al. adopted this method to analyze the fouling behavior during FO of MD.
an aqueous suspension containing bentonite particles. Although OCT
can detect fouling behavior for low pressure processes, it is limited to 2.2.1. Special wettability membranes
detecting thicknesses >3 μm, which makes it difficult to observe dif­ Typically, MD membranes are porous and hydrophobic to prevent
ferences between fouling layers [114]. wetting. In fact, low wetting resistance of existing membranes has
impaired the full-scale implementation of MD systems [116]. At the
same time, hydrophobicity is linked to lower vapor flux. Li et al. [117]
2.2. Membrane distillation
modified quartz fiber membranes with alkylsilane molecules and found
that the least wetting-resistant membrane had double the vapor flux as
When comparing RO to thermal desalination processes which
involve phase change, the lower energy consumption of the former is a
well-known fact. Despite energy consumption increasing with feed
salinity due to greater electrical energy required for the pumps, RO
would energetically still be more feasible than thermal desalination for
treating hypersaline solutions with total dissolved salinity
(TDS) > 50,000 ppm. However, existing commercial RO membranes
cannot physically sustain the high pressures required to desalinate such
solutions (>80 bars). Membrane distillation, which combines extensive
experience in thermal desalination, becomes an attractive choice as
energy consumed does not depend on feed salinity. Advantages of MD
over traditional thermal processes such as MSF and MED include its
compactness, modularity and relatively low heating requirements.
There has been a steady increase in research interest surrounding MD, as
is evidenced by an upward trend in number of publications (see Fig. 5)
on MD.
In MD, a thermal gradient is applied across a membrane separating
the feed and the permeate. The feed is heated and the temperature
gradient across the membrane causes a vapor pressure difference which
forces water on the feed side to evaporate and pass through the mem­
brane pores and condense on the cooler permeate side. Low water flux Fig. 6. DCMD performance of modified quartz fiber membranes: vapor flux and
salt rejection of least wetting-resistant (FAS-17 QF) and most wetting-resistant
and high energy consumption are the two main factors that have pre­
membrane (AS QF) for DCMD. Adapted with permission from [117] Copyright
vented full-scale commercialization of MD. To tackle this, various con­
(2020) American Chemical Society.
figurations have been investigated. Today, four main modes for MD

Fig. 5. Number of publications on ‘membrane distillation’ from 2000 to 2020 (Scopus).

6
F.E. Ahmed et al.
the most wetting-resistant membrane for DCMD using 0.5 M NaCl as
feed (Fig. 6). This trade-off between wetting resistance and vapor flux is
a major factor that has led scientists to explore membranes with special
wettability [118].
Feed water composition strongly affects wetting propensity [119]:
the presence of organics and oils increases wetting propensity, high­
lighting the importance of appropriate pretreatment methods to remove
these before MD. Special wettability membranes include super­
hydrophobic, omniphobic and dual layer hydrophilic-hydrophobic sur­
faces. Shon’s group have recently presented a systematic on special
wettability membranes where they identify fabrication methods for
special wettability membranes, classifying them as nanocomposite
membranes, surface-modified commercial membranes, synthesized
membranes and ceramic membranes [118].
Studies involving superhydrophobic [120–122] and omniphobic
modification of membranes have recently shown enhanced resistance to
challenging feeds containing organics and oils. Embedding nano­
materials for enhancing the hydrophobicity of membranes for MD
[123]. Xie et al. [124] spray coated CNTs on three different substrates:
polytetrafluoroethylene (PTFE), polypropylene (PP) and polyvinylidene
fluoride (PVDF), to improve hydrophobicity. They found that the
packing density of the CNTs decreases with decreasing surface free en­
ergy of the substrate. CNT-enhanced PTFE membrane exhibited a water
flux of 33.2 L m− 2 h− 1, which was three times higher than that of pristine
PTFE. Wang et al. [125] incorporated a CNT layer on a commercial
PVDF membrane followed with FAS grafting, allowing a water contact
angle of 180◦ . The resulting membrane showed high wetting resistance
against 0.4 mM SDS during DCMD, attributed to the CNT intermediate
layer.
Li et al. [121] fabricated a superhydrophobic PDTS-ZnO-PVDF
membrane through fluorination of ZnO blended electrospun PVDF
membrane. Wetting resistance depended on the type of ions present in
the feed with CaSO4 and SDS accelerating membrane wetting.
An obvious approach to attempting to increase the water flux is
modifying membrane design. Hydrophobic membranes, used for MD to
prevent wetting suffer from low water flux. While the barrier layer in
contact with the feed solution must be resistant to wetting, hydropho­
bicity is not desirable vis à vis vapor flux and anti-fouling. This has
prompted much work into dual-layer hydrophilic-hydrophobic. A dual
layer hydrophilic—on-hydrophobic membrane consists of a thin hy­
drophobic layer in direct contact with the feed, and a porous hydrophilic
layer. The hydrophobic layer prevents penetration of saline water
through the membrane, while the porous hydrophilic layer provides
mechanical strength, prevents conductive heat loss, enhances vapor flux
and limits fouling [126]. Hydrophilic-hydrophobic composite structures
were first proposed for desalination via MD in 2005 [127,128]. Each of
these studies employed a different dual layer structure: hydrophilic-on-
hydrophobic and hydrophobic-on-hydrophilic, differing in which layer
was in contact with the feed. Soon after, Chung’s group in Singapore
fabricated dual layer hollow fibers by applying co-extrusion spinning
[126]. Qtaishat et al. [129] reported the first mathematical model to
study the dual layer composite membrane concept in MD as a guideline
towards efficient MD membrane design. Their group optimized mem­
brane preparation parameters and fabricated various hydrophobic-
hydrophilic membrane materials for DCMD [130–132]. From 2010 to
2020, different groups have fabricated hydrophilic-hydrophobic mem­
branes using different materials and fabrication techniques. Recently,
Zhang et al. [133] reported a 326% flux enhancement through a
polydopamine-based hydrophilic surface coating on a commercial PTFE
membrane for VMD of seawater heated to 70 ◦ C.
Sharma et al. [134] applied plasma polymerization to modify the
surface of PP and PES hollow fiber membranes. For MD using
10,000 ppm, PES-based membranes performed better while the PP
substrates were said to have a long vapor diffusion path and hence lower
flux. In an advancement of dual layer membranes, Zou et al. [135]
studied the effect of thickness of the water-intrudable hydrophilic layer
7
Desalination 517 (2021) 115183
during DCMD on membrane performance using hollow fiber membranes
based on a PVDF/polyethylene glycol (PEG) inner layer and a PVDF
outer layer . They found that the hydrophilic layer thickness depends on
membrane pore size, effective porosity and applied hydraulic pressure.
Their findings indicate that a thicker hydrophilic layer exhibited greater
permeate flux and energy efficiency.
Zou et al. [136] fabricated crosslinked PVDF-based hollow-fiber
membranes with dual wettability. Both layers were made by spinning
PVDF, and a PVDF/PEG blend was used for fabrication of the thick
hydrophilic layer. The dope solution for spinning was made of PVDF/
ammonium/water with different ammonium and water content. They
reported exceptional performance with flux as high as 97.6 kg m− 2 h− 1
and 99.9% rejection for seawater desalination.
Chen et al. [137] fabricated ultrathin dense hydrophilic layers of
polyethyleneimine and anionic poly(sodium 4-styrenesulfonate) poly­
electrolytes on a hydrophobic PVDF substrate via layer-by-layer as­
sembly. They found that the number of polyelectrolyte layers were more
important in determining anti-wetting properties of the membrane than
surface wettability or surface charge. An ultrathin hydrophilic multi­
layer of 48 nm was found to have a small enough pore size to reject
surfactant molecules and therefore protect the hydrophobic layer.
Researchers continue to pursue breakthroughs in membrane design
by using novel structures, materials and fabrication methods. Dual layer
membrane structures have thus far shown promising results [138,139].
However, most studies have been carried out using aqueous NaCl solu­
tions with induced wetting. Seawater contains different kinds of ions
and foulants whose effect on special wettability membranes is unclear.
Yin et al. [140] addressed this by comparing a hydrophobic membrane,
hydrophilic-hydrophobic membrane and a superhydrophobic mem­
brane with respect to gypsum and silica scaling in MD. They found that a
superhydrophobic surface is favorable in preventing gypsum scaling,
and water recovery/scaling reversibility increases with increasing hy­
drophobicity. On the other hand, propensity of silica scaling was not
altered by changing membrane wettability. Although flux is a key per­
formance parameter, more studies need to be conducted with natural
seawater or commonly occurring scalants and fouling to form a deeper
understanding of membrane performance and wettability. Together
with theoretical studies [141], advances in wettability of MD membrane
materials, especially for real-life systems will facilitate full-scale
implementation of MD for desalination and brine treatment.
2.2.2. Real-time monitoring and control in MD
In situ detection techniques used for MD have been based on optical
or electrical methods. Jacob et al. developed an in situ tool based on
light transmission and optical properties of the membrane to detect
wetting of membrane pores [144]. Chen et al. [145] used developed a
method based on measurement of cross-membrane impedance for
monitoring the dynamics of pore wetting. Our group also developed a
simple membrane-based electrical method for early detection of wetting
in DCMD [146].
Fortunato et al. [147] found that in situ monitoring with OCT
coupled with membrane autopsy improved understanding of fouling
mechanism and appropriate sampling time. The same technique of OCT
was also employed by Bauer et al. [148] and Lee et al. [149] as an early
detection and imaging tool for in situ visualization and quantification of
scaling in a fully operated DCMD system. They found that the feed
spacer does not necessarily trigger scaling. Kiefer et al. applied an
incident light microscopy in conjunction with an image processing
strategy setup to monitor crystal growth and scale formation on the
membrane during vacuum MD [150]. The image processing strategy,
Digitally Simulated Dark Field Illumination, assisted the process by
overcoming the low contrast between crystals and membrane surface.
Lokare et al. [151] applied a laser-based spectrophotometric method for
in situ characterization of the concentration polarization layer in MD.
Shin et al. [152] apply ohmic heating to heat an aqueous feed so­
lution to 70 ◦ C without consuming external electrical energy for DCMD.
F.E. Ahmed et al.
Feed solution was passed through an electrochemical reactor before
entering and after exiting the feed channel of the MD cell. The electro­
chemical system consisted of a Ti cathode and a boron doped diamond
(BDD) anode, each 30 cm2 and separated from each other by 1 cm. Fig. 7
shows a schematic of their experimental setup. The system was com­
bined with electrochemical oxidation (EO), which they referred to as an
EO-DCMD hybrid, whereby Ohmic heating along with anodic persulfate
formation from the sulfate degraded the foulant (alginate). The effect of
applying electrochemical oxidation on flux with and without alginate is
shown in Fig. 7b. Intermittent gas bubbling has also been proposed as a
fouling control strategy for MD. In recent years, the use of intermittent
gas bubbling for fouling control in MD has been explored by a few
groups. One of the first studies involved intermittent gas bubbling to
reduce fouling for an MD system targeting the concentration of tradi­
tional Chinese medicine [153]. A process optimization study by Rong
Wang’s group showed that flux enhancement via bubbling was higher
when a higher feed temperature, lower feed and permeate velocities and
shorter hollow fiber lengths are used [154]. Meng et al. found that
bubble generation could actually increase salt deposition when the feed
solution contained sparingly soluble salts. This demonstrates the need
for further development in this area with a focus on process optimization
and investigation of feed and operating conditions that promote fouling
control with bubbling. Warsinger et al. developed a new method
involving air layers on a surface-modified superhydrophobic membrane
surfaces to prevent fouling by salts, particulates and organic particles
[155].
2.3. Electrochemical desalination
Electrochemical desalination systems remove salt ions from feed
solutions through electromigration and electrosorption. Two of the most
commonly employed electrochemical desalination processes in industry
today are ED and CDI, both of which have been around for >50 years.
Researchers have, up until recently, sought to address the shortcomings
of these technologies with the objective of competing with RO desali­
nation in terms of performance, cost and energy consumption. Limita­
tions of each of these processes has prevented them from competing with
thermal and RO desalination; however, exciting material-driven
research in just the last decade has led to promising developments,
which may raise the importance of electrochemical desalination pro­
cesses in the near future. Fig. 8 shows the increase in number of publi­
cations on electrochemical desalination in the last 20 years.
In recent years, emerging technologies based on novel materials and
system design could be revolutionizing electrochemical desalination. To
Fig. 7. (a) Experimental Setup of the EO–DCMD Hybrid Process; (b) Effect of alginate on DCMD and EO-DCMD hybrid system performance. Adapted with permission
from [152]. Copyright (2020) American Chemical Society.
8
Desalination 517 (2021) 115183
better understand emerging technologies, we first consider existing
electrochemical desalination processes i.e. ED and CDI, and their limi­
tations. This helps set the stage for discussing exciting advances in
electrochemical desalination, which include, multi-stage configuration,
high-capacity electrodes and the ‘desalination battery’,
2.3.1. Electrodialysis
In an electrodialysis system, an electric field is applied across two
electrodes and a resulting ionic current causes the migration of anions
and cations to the positive and negative electrodes, respectively. The
ions are met with a stack of alternately placed anion exchange mem­
branes (AEM) and cation exchange membranes (CEM), which selectively
transport one type of ions. This results in channels with low concen­
tration solution, from which ions have been removed, and channels with
high concentration solution in which similarly charged ions accumulate
(see Fig. 9).
For efficient ED, ion exchange membranes (IEM) should exhibit high
permselectivity, low electrical resistance and high mechanical and
thermal stability [157]. An assembly of an AEM and a CEM and adjacent
flow channels is referred to as a cell pair [158]; the number of cell pairs
making up an ED stack or module can vary from a few at the laboratory
scale, to several hundred for industrial use [159].
The very first seawater desalination plant using ED installed in 1974
had a capacity of 120 m3/day and consumed 16.21 kWh/m3 [160].
However, despite being an established desalination technology, ED
makes up a relatively small share of total desalination capacity. Indus­
trial use of ED is largely limited to low salinity feed solutions such as
brackish water. This is because the energy required for ED increases with
increasing concentration of ions in the feed solution. Another factor that
has hindered more widespread use of ED is the high cost of IEMs
compared to RO membranes [159]. With the revival of electro­
membrane processes, attempts at novel system designs of ED systems
have targeted: 1) competitive seawater desalination, and 2) salt recov­
ery for brine treatment, both of which are reviewed in this section. In
particular, RevivED water is research project funded by the EU that
focuses on developing ED as a competitive technology for seawater
desalination.
2.3.1.1. Electrodialysis for seawater desalination
2.3.1.1.1. Multi-stage electrodialysis. Energy consumption is the
main deterrent to the commercial use of electrodialysis for seawater
desalination, as mentioned earlier. Energy consumption can be lowered
by increasing system size, but this only holds true up until a certain
critical size after which losses due to osmosis and diffusion catch up
F.E. Ahmed et al.
Fig. 8. Number of publications on ‘electrochemical desalination’ from 2000 to 2020 (Scopus).
Fig. 9. Schematic of an electrodialysis module [156].
[161]. With staging, the feed and flow conditions at a specific stage
govern the energy required for desalination to the desired level within
that stage. When the total area of the system is fixed and the outlet sa­
linities for each stage are predetermined, the voltage to achieve the
desired permeate quality can be optimized for each stage. Fig. 10 shows
a schematic of a simple two-stage ED system where V1 and V2 are the
voltages applied to each stage, and A1 and A2 are the areas of the first
and second stages respectively.
Fig. 10. Schematic of simple two-stage electrodialysis system with brine
recirculation [161].
9
Desalination 517 (2021) 115183
Multistage ED was first studied in 1999 by Cruz et al. [162], for the
separation of metal ions. In the years that followed, a few studies
investigated the performance of multistage ED systems for different
applications, including pretreatment [163] and softening of seawater
[164]. Both studies target the removal of divalent ions, as a greater
removal of divalent ions from seawater is favorable at a low applied
current density, due to the concentration polarization effects in the
diffusional boundary layer [164]. In 2003, Turek applied a two-stage ED
system for the desalination of artificial seawater, at a current density of
300–600 A/m2 in the first stage, and 300 A/m2 in the second, and ob­
tained drinkable water in the diluate (TDS 540 ppm) with a specific
energy consumption of 6.6 kW/m3 [165]. Zhang et al. applied a three-
stage batch ED system to separate divalent ions from seawater concen­
trate, producing coarse salt with a purity of 85% under continuous
operation [166]. Soon after, Yan et al. concentrated a 35,000 ppm NaCl
solution to 206,000 ppm using a three-stage ED with SEC of 12.34 kWh/
m3 [167]. However, these studies focused on concentrating seawater to
get high purity salt, and not as much as generating potable water. Since
Turek’s work, only Kitty Nijmeijer’s research group has investigated the
viability of multistage ED for seawater desalination [168–170],
comparing it with single stage ED and a new segmented electrode
configuration [171]. They argue that by using a multistage system, each
stage can operate at its individual optimum depending on the governing
conditions at that stage [170]. To produce drinkable water (TDS
500 ppm) from brackish water at 11,000 ppm, there was not much dif­
ference in terms of energy consumption between the single stage and
multistage ED configurations. However, for higher salinity feeds,
multistage ED had a clear advantage. They optimized membrane area,
residence time of the ions in each stage and membrane permeability for
multistage-ED. Residence time is the time that ions have to pass through
the membranes. A high flow velocity equates to lower residence time
and lower salt flux. A high current density increases the driving force for
electroosmotic flow, which translates into greater salt flux from diluate
to concentrate [170]. They found that, for a four stage ED system, a
longer residence time in the first stages and a shorter residence time in
the later stages is energy efficient. This is because the early stages have
already created a concentrate gradient between diluate and a longer
residence time would only increase unwanted osmotic losses [169].
They also varied flow velocity and membrane permeability in the later
stages and found that energy consumption could be reduced to 2.2 kWh/
m3, making it competitive with RO technologies. When the group tested
their 4-stage ED system using natural seawater as feed over a period of
18 days, and were able to desalinate seawater from an initial concen­
tration of 27,000 ppm to 1900 ppm, consuming 3 kWh/m3 [168]. Their
work is part of the REvivED project funded by the EU, which focuses on
developing ED as a competitive technology for seawater desalination.
F.E. Ahmed et al.
2.3.2. Capacitive deionization
Although CDI was introduced in the 1960s, the lack of large-scale
energy efficient plants reflects its status as an emerging technology.
CDI involves applying an electric field to force salt ions to migrate to­
wards oppositely charged electrodes; the electrodes are typically porous
and exhibit a high surface area. Salt ions are adsorbed in the electrical
double layer of the electrodes; this electrical double layer is formed
between the bulk solution and the electrode interface when an electric
field is applied. The salt removal efficiency of CDI systems is strongly
related to electrode material and geometry, among other factors. Ions
are electrostatically adsorbed on the internal surface of the electrode so
greater the electrode surface area, the greater its ion adsorption capac­
ity. When the potential difference is reversed, desorption of the ions
takes place and the electrodes can be regenerated. High electrical con­
ductivity and mechanical stability of the electrodes are also desirable
attributes. Electrode design involves a trade-off between maximizing
surface area for electrosorption while minimizing distance for ions to
migrate across [172]. The absence of suitable electrode materials and
geometries that would provide high ion adsorption capacity and there­
fore high salt removal rates is a key challenge that hinders the practical
implementation of CDI desalination. Although voltage can be increased
to increase salt removal, this also increases energy consumption and
losses due to unwanted side reactions. Conventional CDI systems cannot
be used efficiently for desalination of high salinity feed solutions such as
concentrated brackish water or seawater.
For decades, only porous carbon electrodes were considered for CDI.
Activated carbons, for example, have internal specific areas on the order
of 103 m2/g [173]. Other carbon materials that have been applied to CDI
include carbon aerogels, activated carbon fibers, carbon nanotubes and
graphene have all been applied as CDI electrodes [174,175]. High
manufacturing costs, pure wettability and limited ion adsorption ca­
pacity associated with some carbon materials have garnered an interest
in carbon-based composites consisting of metal oxides or polymers,
where the non‑carbon material is incorporated to improve ion adsorp­
tion capacity and/or add another functionality to the electrode material
[174,176].
2.3.3. Desalination battery: next-generation CDI
Recently, research has focused on non‑carbon materials with greater
Fig. 11. Operating principle of the desalination battery. Reprinted (adapted) with permission from [180]. Copyright (2020) American Chemical Society.
10
Desalination 517 (2021) 115183
adsorption capacity, to increase the energy efficiency of CDI systems. In
particular, the concept of a ‘desalination battery’ that uses high capacity
battery electrode materials has emerged, interest in which has been
steadily rising since its introduction in 2012 by Yi Ciu’s group [177].
Currently, China leads research in this new area (by number of publi­
cations), followed by South Korea and USA.
A desalination battery is similar to CDI in that it uses electrical en­
ergy input to extract salt ions from seawater. However, instead of storing
charge solely on the electrode surface or at the electrode-electrolyte
interface, ions are held in the bulk of the electrode material via chemi­
cal bonding [177]. The use of battery materials, or Faradaic ion inter­
calation materials, distinguishes the desalination battery from CDI and
has also been referred to next-generation CDI where ions are captured in
the bulk of the electrode [178]. The desalination battery consists of Na-
storage and Cl-storage electrodes and the feed or seawater as electrolyte.
When charging, Na+ and Cl− ions are stored in Na+ storage and Cl−
storage electrodes respectively resulting in desalinated water between
them. On the other hand, the ions are released during discharge,
allowing the electrodes to regenerate. Fig. 11 shows the operating
principle of a desalination battery. The use of battery electrode materials
enables high salt-removal capacity and low energy consumption, due to
their high electrochemical capacity and their cyclic energy storage and
discharge capacity which allows for energy recovery [179]. It is evident
that the development of suitable electrode materials with long cycle life
and high salt removal capacity will be key to the development of the
desalination battery in the near future. In addition to electrochemical
capacity, other material properties such as hydrophilicity and solubility
are also key parameters in determining its performance in a desalination
battery. Here we review the types of desalination batteries, material
development and future prospects and challenges associated with
scaling up the desalination battery.
Chen et al. [181,182] applied a sodium manganese oxide
(Na0.44MnO2) as the Na-storage positive electrode in a redox flow bat­
tery desalination system. They have explored the use of both BiOCl and
AgCl as Cl-storage negative electrodes. Faradaic deionization using this
system results in a salt removal efficiency of 68.5 mg g− 1 and
57.4 mg g− 1 for systems with BiOCl and AgCl negative electrodes,
respectively. However, in both cases the feed concentration was kept
under 900 ppm feed concentration. Although the salt removal efficiency
F.E. Ahmed et al.
is reversible and promising, studies must be carried out using higher
concentration feed solutions. The same group has also applied
NaTi2(PO4)3 as an anode with silver electrode as cathode [183]. In the
same year, Wang et al. applied a similar NaTi2(PO4)3 anode and Ag
cathode and demonstrated its ability to be continuously photocharged
with a solar cell, combining the benefits of the desalination battery with
renewable energy [184]. Although Ag electrodes [185] are a popular
Cl− -storage material for batteries and by extension for next generation
CDI systems due to their ability to capture and release Cl− ions, ac­
cording to the reversible reaction Ag+ (aq) + Cl− (aq) ↔ AgCl, researchers
are also exploring novel chloride-storage electrode materials to further
enhance the capacity of desalination batteries for practical use
[186–188].
Another kind of cell architecture is the redox flow desalination bat­
tery. A redox flow desalination battery [180] consists of three com­
partments, divided by the AEM and CEM: one for the anolyte which is
used for chloride release and capture, one for the catholyte which used
for sodium release and capture, and one for the saline feed solution
(Fig. 12). During charging, oxidation at the catholyte enables removal of
Cl− through the AEM. On the other hand, Na+ is removed as it is
captured through the CEM due to a reduction reaction at the anolyte.
During discharging, Na+ and Cl− are released from the catholyte and
anolyte respectively and the two electrolytes are regenerated. Redox
flow desalination batteries are promising for low-energy desalination as
redox reactions at the electrolytes enable voltage suppression and
enhanced salt adsorption capacities.
Beh et al. recently developed four-chambered cell architecture of a
redox flow desalination battery using a solution-phase redox shuttle. A
redox shuttle is an electrolyte additive which can be reversibly oxidized
or reduced at a characteristic potential [190]. Ion motion driven by low
voltages enables energy efficient shuttle prompted desalination of
seawater and hypersaline feed solutions. The authors demonstrate
single-stage desalination of seawater to drinkable water at 192 ppm at
4.91 kWh/m3, comparable to the energy consumption of RO units. In
another redox flow desalination battery, Kim et al. used the redox couple
of ferricyanide/ferrocyanide in addition to conventional carbon elec­
trodes to enhance salt removal capacity. With the redox reaction, salt
adsorption capacity increased from 19.9 to 67.8 mg g− 1. Ferrocyanide is
oxidized whereas ferricyanide is reduced, the combination of which
results in constant transfer of cations and anions from the dilute stream
to their respective concentrate streams. These redox reactions occur at
low operating potentials (~100 mV), making it possible to desalinate
with low energy consumption [191].
Another type of desalination battery is the rocking chair desalination
battery in which both electrodes are either Na- storage or Cl- storage.
When Na- storage electrodes are used, an anion exchange membrane
separates the system into two components. During charging, cations in
the negative compartment solution are electrochemically captured by
Fig. 12. Schematic of a redox flow desalination battery [189].
11
Desalination 517 (2021) 115183
the anion, and cations already present in the positive electrode are
released to the solution in the positive compartment. Anions from the
negative compartment are allowed to pass through the AEM into the
positive compartment, thus forming a concentrated stream in the posi­
tive compartment and a diluted stream in the negative compartment.
The treated water is then exchanged with more of the feed source and
dilution and a voltage is applied again to reverse the movement of ions
during discharge. A schematic description of the rocking chair desali­
nation battery is shown in Fig. 13.
Bruce Logan’s group applied two identical copper hexacyanoferrate
(CuHCF) battery electrodes for storing and releasing cations in a rocking
chair desalination battery. At a low applied voltage of 0.6 V, they ach­
ieved desalination capacities of up to 100 mg-NaCl/g-electrode [193].
To put this in perspective, typical values for carbon-based electrodes in
CDI systems are between 10 and 15 mg g− 1 electrode [181,194]. How­
ever, they used a low feed NaCl concentration of under 3000 ppm. In
another study, Chang et al. [195] also used a CuHCF electrode coupled
with an activated carbon (AC) electrode for desalination of brackish
water with TDS 10,000 ppm, achieving a salt removal efficiency of 91%
vs. 84% for an AC-AC pair of electrodes . Such systems made of one
battery electrode and one capacitive electrode are referred to as hybrid
capacitive deionization (HCDI) [178].
In another demonstration of a rocking chair desalination battery,
both Volker Presser’s group [196] from Germany and Jeyong Yoon’s
group [197] in South Korea applied Ag/AgCl electrodes with a cation
exchange membrane system where Na+ is passed through the CEM to the
negative compartment solution and Cl− ions are released by the AgCl
electrode and captured by the Ag electrode, to continuously produce
desalinated water. For a feed solution of 500 mM NaCl (almost
29,220 ppm), Yoon’s research group reported a desalination capacity of
85 mg g− 1 with an 80% salt removal ratio. They suggested that using
identical two-phase reaction electrodes reduced the cell voltage
required to desalinate to <0.2 V. Presser’s group reported a desalination
capacity of 115 mg g− 1 for a higher feed solution (TDS 35,000 ppm)
using the same cell voltage.
Prussian blue (PB) and its analogues (PBAs) are also a promising
class of materials for electrochemical energy storage devices, given their
high charge capacity, long life cycle and reversible reaction. Their
nanoporous and open-framework allows them to react with several
alkaline ions present in seawater [198–200]. Lee et al. [192] recently
developed a rocking chair desalination battery based on Prussian Blue
materials. Sodium nickel hexacyanoferrate (NaNiHCF) and sodium iron
HCF (NaFeHCF) electrodes were applied for the desalination of
seawater. They reported a desalination capacity of 59.9 mg g− 1 and an
energy consumption of 0.35 Wh/L for 40% Na ion removal.
It is evident that progress is being made towards new high capacity
battery materials for next-generation CDI systems or desalination bat­
teries. Not all battery materials can be applied to desalination: the
electrodes’ close contact with aqueous solution means that the material
must be insoluble, hydrophilic and redox reactions must prevent water
splitting and instead, focus on salt removal. Additionally, the hydration
effect of ions in water may make it more challenging for these materials
to act as desalination battery electrodes. At present, we have yet to see
comparison of this technology with existing processes. More work is
needed to estimate the energy efficiency of these systems, especially at
larger scale, to see where it stands among desalination processes and
whether it can break the barriers faced by CDI.
3. Technology status
The development of any technology towards maturity is at least
partially driven by energy consumption. In this section, we consider the
current status of the emerging technologies discussed above, considering
key factors such as energy consumption, technology readiness, efforts to
improve technology readiness and associated limitations. We also
consider technological readiness level (TRL), which is an indicator of
F.E. Ahmed et al.
Fig. 13. Operating principle of a rocking chair desalination battery [192].
maturity of a particular technology. TRL is measured on a scale from 1 to
9, 1 being the lowest and 9 being the highest [201]. A TRL of 9 reflects
the implementation of an actual system in operational environment.
3.1. Forward osmosis
Forward osmosis itself is a low energy process in which a low-
pressure pump is used to overcome the pressure drop in the feed chan­
nel. It has been reported that the osmosis step consumes roughly be­
tween 0.10 and 0.55 kWh/m3 [202]. However, depending on the
method applied for draw solute recovery, the energy of an FO desali­
nation system is between 3 and 8 kWh/m3 [202]. One suggested method
to keep energy consumption low is by using fertilizer in the draw solu­
tion in a process known as fertilizer drawn forward osmosis (FDFO)
[203]. In FDFO, commercially available soluble fertilizers can be used as
high osmotic pressure draw solutions whereby the diluted draw solution
resulting from forward osmosis can be directly applied to fertigation,
eliminating the need for draw solution recovery [203,204]. However, in
some cases, post-treatment NF still needs to be applied to reduce the
nutrient concentration to make it suitable for irrigation [58]. In addition
to high performing water permeable membranes, the development of FO
is linked to optimizing module design and packing density [205].
Currently, several global suppliers of FO membranes exist, with some
products still in the development stage [58]. The first plant was built in
2010, and several pilot scale demonstrations have followed, but large-
scale FO plants have yet to materialize.
Im and Jang [206] compared the performance and cost of three
commercial-size spiral wound TFC-FO membrane elements of different
areas and found that the large membrane was 24% more cost-efficient
than the small one. Table 6 shows the specifications of the three types
of elements. Their study was motivated by the need to evaluate element
size and structural factors on membrane performance and water pro­
duction cost.
A recent survey of 15 pilot scale installations showed that energy
consumption arising from the draw solution recovery is hindering full-
scale implementation [58]. To make FO competitive with RO
12
Desalination 517 (2021) 115183
desalination, energy consumption for the draw solution recovery step
must be reduced by 40-50%. Other alternatives are to apply FO for os­
motic concentration or FDFO, and therefore without draw solution re­
covery step, or in competition with high energy consuming thermal
desalination processes. The aforementioned survey included 15 FO in­
stallations based on either seawater/brackish water desalination,
wastewater treatment or oil and gas effluent treatment. Eight of these
projects employed NaCl as the DS at a concentration ranging between 26
and 35 g/L for wastewater and between 39 and 260 g/L for brackish
water, seawater and produced water feeds, and RO was used to recover
the DS. Pilot-scale demonstrations have shown an energy reduction
when FO desalination is combined with wastewater reclamation [58].
Since Awad’s survey, Forward Water Technologies Inc. have re­
ported a full-scale trial of their FO plant in Airdrie, Canada for desali­
nation of wastewater [207]. However, as Khan highlights, details on
full-scale trials are often difficult to find due to commercial sensitivity
[208].
3.2. Membrane distillation
As of 2016, MD was also classified as a low TRL technology [209].
With the objective of driving the TRL to a higher value, 12 pilot-scale
investigations have been carried out between 2010 and 2020 in
various locations, using technology for different developers [210]. PTFE
is the most common membrane material in these studies. DCMD systems
have a lower thermal energy efficiency compared to other configura­
tions such as VMD and air gap MD (AGMD) due to greater conductive
heat losses from the membrane. Nevertheless, DCMD still makes for a
suitable choice for lab-scale testing due to its simple design. However,
because MD is a phase change process, the energy consumption is orders
of magnitude higher than that for pressure-driven desalination pro­
cesses. Successful full-scale implementation of MD must ensure the use
of waste or renewable energy for heating. Some pilot-scale studies have
investigated the use of solar energy [211–213]. Research projects such
as SolMed, “Desalination by Solar Powered Membrane Distillation:
Material and Process Optimization” [213] funded by the European
F.E. Ahmed et al.
Regional Development Fund have been crucial in supporting MD
research from lab to pilot scale, especially in Europe.
Table 7 shows existing technology developers for MD, as reviewed by
Hussain et al. [210].
A 2016 report published on a workshop at Massachussetts Institute of
Technology (MIT) identifies the TRL for both MD and FO at under 5
which is classified as low TRL. However, an increasing number of pilot-
scale studies for both technologies is likely to have driven the TRL for
both technologies to higher levels. Similar to FO, module stacking and
exploration of multi-stage MD units would lead to further improvements
in the performance of MD systems and enable more full-scale plants.
There also remains limited research into using condensation energy to
heat incoming feed, which would significantly improve energy effi­
ciency of MD systems [214].
3.3. Electrochemical desalination
CDI is not applied to desalination of highly saline feed solutions
mainly due to two factors: first, existing electrode materials have low ion
capacity (<30 mg g− 1) which severely limits salt rejection in CDI; sec­
ond, the energy consumption is highly sensitive to feed salinity (see
Fig. 14A). Salt rejection is also limited by cell voltage that needs to be
low enough to prevent undesirable Faradaic reactions. Consequently,
maximum salt rejection for desalination of 5000 ppm and 10,000 ppm
feeds were restricted to 55% and 28%, respectively [215]. Qin’s group
pointed out that the energy efficiency of CDI does not depend on salt
rejection, although energy efficiency for RO systems increases with
increasing salt rejection (Fig. 14B–C). This translates into CDI being
energetically preferred only for low salt rejection (<25%) and low
Fig. 14. (A) Impact of feed salinity and salt rejection on the specific energy consumption of CDI; Effect of salt rejection and average water flux on energy efficiency
for (B) CDI and (C) RO for brackish water desalination [215].
13
Desalination 517 (2021) 115183
average water flux (~10 L m− 2 h− 1) [215]. Soon after, another group
commented that values of energy consumption estimated by Qin were
very high [216], to which Qin et al. responded to by applying an
alternate method to reach the same conclusion [217].
Recently, the use of energy recovery systems have shown to reduce
specific energy consumption of pilot scale CDI systems by 30-40%
[218,219]. Many commercially available CDI systems have been applied
to small brackish water desalination plants, as pointed out by Nicolas
Voutchkov [220]. However, the lack of high capacity electrodes and
relatively high energy consumption have been a challenge in their large-
scale applicability to brackish water desalination, where RO still dom­
inates. Desalination batteries, with significantly higher ion capacity,
could break the barrier in the large-scale implementation of CDI for
brackish water desalination. However, as pointed out earlier, research in
this area is still in early stages with little to no data on energy con­
sumption of these systems. Zavahir et al. recently compared the TRL of
electrochemical systems, specifically for Li removal [221]. Most CDI
processes remain at a TRL of under 5, whereas a few ED systems have
reached TRL 7. This was attributed to the high capital cost and mediocre
desorption efficiency of CDI systems.
As Mauter and Fiske point out, funding and support of low TRL
innovation at all levels is crucial to driving early stage technologies
towards commercialization [222]. Table 8 compares select emerging
desalination technologies with reverse osmosis for seawater desalina­
tion. It should be pointed out that the energy consumption listed for RO
is a large-scale RO plant, whereas that for the other technologies is for
bench scale modules, making a fair comparison challenging. Table 9
provides an overview of recent pilot-scale studies employing FO, MD
and ED desalination.\.
F.E. Ahmed et al. Desalination 517 (2021) 115183

4. Future work Table 2

Selected materials and fabrication techniques used fabrication and modification
Presented below in Table 10 are the aspects that were found to be the of FO support layer.
most important as shown by research publications between 2017 and Support material Fabrication method Reference
2021. While membrane development remains the single most significant Polydopamine-coated nanofiber Deposition on [95]
area of research, literature from the last five years shows a shift to electrospun mat
exploring process improvement strategies such as fouling characteriza­ Polycarbonate Non-solvent induced [67,94]
tion and control, heat recovery and effects of upscaling as a means to phase separation
Polyvinyl alcohol hydrogel Non-solvent induced [96]
improve energy efficiency. In this section, we consider hybrid desali­
phase separation
nation systems and low-carbon desalination using renewable energy as Cellulose acetate-polyvinylidene fluoride Coaxial electrospinning [97]
important future directions for desalination. (PVDF)
Polyethersulfone (PES) Non-solvent induced [98]
phase separation
4.1. Hybrid desalination technologies Polyvinyl alcohol Coating on electrospun [99]
substrate
Polysulfone/polyacrylonitrile blend Electrospinning [100]
One promising direction taken by research in emerging desalination
Polyphenylensulfone (PPSU)/cellulose Non-solvent induced [101]
technologies involves the hybridization of two or more processes. The acetate phthalate (CAP)/functionalized phase separation
goal of hybridization is to improve the overall efficiency of desalination multiwalled carbon nanotube
plants by overcoming drawbacks of individual systems and achieving (FMWCNT) membrane support
comparative advantage [230]. Initially, hybrid desalination systems
referred only to thermal-RO systems, eg. MSF-RO and MED-RO; how­
process feasible. The FO step simultaneously treats wastewater and di­
ever, recent literature shows numerous possibilities for hybrid systems.
lutes the seawater draw solution, lowering the operating pressure for RO
In this section, we discuss hybrid systems based on the three types of
to desalinate seawater [33,205]. Although the capital cost of this hybrid
emerging desalination previously discussed.
system is higher than SWRO alone, the hybrid system demonstrates 56%
Because forward osmosis does not directly produce desalted water,
lower OPEX compared to SWRO due to energy savings [205].
but instead requires a regeneration step to further separate water from
MD in particular is promising for hybridization with RO or FO for
the draw solution, it is an obvious choice for hybridization with other
resource recovery as it can be used to treat highly saline solutions
processes. The cost of desalination with FO depends strongly on the
without compromising separation performance. Many studies have
method chosen for draw solute recovery, making the design of hybrid FO
focused on wastewater treatment, nutrient recovery and/or brine con­
systems a key factor in determining the cost of desalinated water. While
centration using FO-MD hybrid systems [231–239], In most hybrid
RO can be used to regenerate high osmotic pressure draw solutions,
systems, the product of one process becomes the feed to the other, with
hybridization of FO and RO is not beneficial for seawater desalination
both processes taking place in separate modules. Cath et al. were the first
from an energy savings standpoint. This is because the osmotic pressure
to design an integrated MD module [240,241], after which FO-MD
of the draw solution must be greater than that of the feed, i.e. seawater,
module designs were further upgraded to ensure minimal heat loss
requiring energy consumption for RO to recover the draw solution to be
and high efficiency of each process [242]. Fig. 15 shows a schematic of
greater than that for seawater desalination with RO alone. Integration of
an FO-MD module with flow directions indicated.
FO with low-pressure RO has however been suggested by using FO to
Nguyen et al. used a mixed trivalent draw solution to achieve a water
treat incoming wastewater with seawater as the draw solution, in a
flux of 6.12 L m− 2 with brackish water (TDS = 5000 ppm) as feed [243].
strategic choice of feed and draw solutions to make an FO-RO hybrid
The draw solution was then recovered using MD with a high salt
rejection of 99.99% at a feed temperature of just 55 ◦ C. Similarly, Li
Table 1 et al. [244] applied an FO-MD hybrid system to concentrate textile
Summary of materials and fabrication techniques for modification of FO active wastewater by 10 times towards achieving ZLD. Arcanjo et al. [235]
layer with nanomaterials.
studied five different draw solutions and their effect on permeate flux
Modification Fabrication method Effect Reference and trace organic compound (TrOC) removal in a submerged FO-MD
Zeolite nanoparticles in Interfacial Near doubling of [69] hybrid system for wastewater treatment. They found that MgCl2 as DS
PA layer polymerization pure water flux produced the lowest reverse salt flux during FO.
Super-hydrophilic Interfacial 52% increase in [72] ED hybrid systems aim to either increase overall water recovery of
zirconium (IV)- polymerization water
carboxylate metal- permeability at
another desalination process, or to concentrate streams for near-ZLD.
organic framework 0.1 wt% Zhang et al. [245] recently explored the near-ZLD of desulfurization
(MOF) UiO-66 nanoparticle wastewater using an ED-RO hybrid system, concentrating the stream
nanoparticles in the loading from 78 g/L to >230 g/L, while simultaneously achieving a low
PA layer
permeate conductivity of ≤550 μS/cm. Moazeni and Khazaei found that
Incorporated nano- Interfacial Improved flux and [73,74]
sized silver-based polymerization resistance to an integrated module reduces energy peak demands by >30% [246].
MOFs to PA biofouling However, a previous study by Thampy et al. [247] showed that the ED-
membranes RO hybrid system for brackish water desalination consumes more en­
CNTs interlayer CNTs airbrushed Water flux [75] ergy than standalone RO. In their system, ED was applied in the high
between the PA onto electrospun increased by 84%;
active layer and PAN support before Reduction of
salinity region as pretreatment to RO as the separation efficiency of ED
electrospun interfacial reverse salt flux systems is proportional the feed concentration. This enabled the RO unit
polyacrylonitrile polymerization by 76% to be fed with a lower salinity feed, with a lower osmotic pressure.
(PAN) support.
CNTs as the interlayer Interfacial Enhanced water [77]
4.2. Low-carbon desalination
and incorporated polymerization flux
silver decorated
graphene oxide Despite making rapid advances towards energy-efficient desalina­
quantum dots tion, desalination processes remain energy-intensive and are also a
(GOQD) into PA source of considerable greenhouse gas (GHG) emissions. The carbon
layer.
footprint of SWRO, although lower than thermal processes, can be as

14
F.E. Ahmed et al. Desalination 517 (2021) 115183

Table 3
Typical draw solutions and corresponding characteristics used in FO processes [102].
2
Draw solute Typical concentration range (M) Osmotic pressure range (atm) Molecular weight (g/mol) Water flux range (L m− h− 1) Approximate unitary cost ($/kg)

NaCl 0.5–5 25–250 58.5 5–45 10–15

KCl 0.5–5 20–230 74.6 3–40 35–40
MgCl2 1–5 100–1150 95.2 8–30 25–30
CaCl2 1–5 100–1100 111 8–30 35–40
NH4HCO3 0.5–5 20–100 79.1 5–25 45–50

to be connected to the power grid and/or energy storage devices [252].

Table 4
Fig. 16 shows an overview of the types of energy from different
Challenges in MD and corresponding approaches adopted in literature.
renewable energy sources for RO, FO, MD and ED. To date, the most
Challenge Recent approaches common combination is the integration of photovoltaics with RO (PV-
Low water flux • Nanoparticles embedded in RO). In a recent review on RO driven by wind and solar energy, Mito
membrane et al. identified shortened membrane life as a technical challenge of
• Graphene membranes
integrating RO with renewable energy systems, particularly solar and
• Special wettability
Temperature polarization • Spacers
wind energy. Reduced membrane life can result from intermittent
• Alternative heating techniques
Monitoring of wetting, fouling and scaling • Electrical methods
phenomena • Optical methods Table 6
Control of fouling and scaling • Bubbling Specifications for spiral wound membrane elements of different sizes [206].
• Electrochemical oxidation
Element scale 2540 4040 8040

Effective membrane area (m2) 1 3.1 15.3

high as 6.7 kg CO2 eq/m3 [248]. For this reason, the decision to build a Membrane material Polyamide thin-film composite
desalination plant is sometimes met with resistance from environmental Feed: Corrugated polystyrene/2.5 mm
Spacer
Draw: Tricot (dense/rigid)/1.5 mm
groups and residents. Low-carbon technologies are likely to play an Number of leaves (ea) 3 7 10
important role in lowering the environmental footprint of desalination 1.12 and 1.20 and 1.44 and
FS and DS flow path height (mm)
and also driving public acceptance of desalination. 1.0 1.0 1.15
Dimension Length × diameter (mm) 960 × 64 963 × 102 963 × 201
Membrane intrinsic properties (A, B A (Lm− 2 h− 1 bar− 1): 5.37–5.4 B (L m− 2 h− 1):
4.2.1. Renewable energy desalination
and S value) 0.64–0.971 S (μm): 220–254
Integration of renewable energy is an important step in the decar­
bonization of desalination processes, driven not only by the high carbon
footprint of desalination processes, but also the limited availability of
Table 7
fossil fuels. Growing regulations on GHG emissions has amplified the
MD technology developers [210].
role of renewable energy to power desalination systems [249,250].
Renewable energy sources studied for desalination include solar, wind, Developer Membrane MD system Country
configuration configuration
geothermal, tidal and hybrid systems. Of these, solar powered desali­
nation systems have been most intensively studied due to rapid growth Fraunhofer Spiral wound Air gap Germany
SolarSpring Spiral wound Air gap Germany
in solar energy technologies. Another factor that makes solar energy
Scarab/Xzero Flat sheet Air gap Sweden
attractive for desalination processes is the high solar irradiance in water TNO/Memstill Proprietary Air gap Netherlands
stressed-regions. Solar energy is also adaptable in that it can be extracted Memsys GmbH Flat sheet Vacuum air gap Germany,
in the form of electrical energy (photovoltaics) or thermal energy (solar China
collectors) depending on the demand of the desalination process. Keppel/ Flat sheet Air gap and DCMD Singapore
Memstill
Despite the growth of solar energy, its contribution in desalination re­
Aquatech Flat sheet Vacuum USA
mains <0.02% [251]. KmX Hollow fiber Vacuum Canada, USA
Energy for desalination can be obtained from renewable sources as corporation
thermal energy, electricity or mechanical energy. As some renewable Econity Hollyow fiber Vacuum Korea
Memsift Hollow fiber Vacuum (Joule Singapore
energy sources are not able to generate electricity in a stable or
Innovation Thomson)
continuous way, renewable energy desalination systems may still need

Table 5
Performance of selected dual layer membranes for MD desalination.
Membrane Fabrication method MD operating Performance Ref.
conditions

Triple-layer PVDF-PTFE hydrophobic layer, a PET support layer, and Electrospinning DCMD Hydrophilic layer increases flux by 26% [139]
a chitosan-polyethylene oxide (CS-PEO) hydrophilic layer
VMD
Surface coating on Membrane flux increases 4 fold from neat
Polydopamine (PDA)/polytetrafluoroethylene (PTFE) Feed: 3.5 wt% [133]
commercial PTFE membrane PTFE
NaCl, 70 ◦ C
PVDF/SiO2 Dry-wet phase inversion VMD Addition of 6 wt% SiO2 increases flux 18-fold [142]
Polyelectrolytes enhance resistance to SDS
Polyelectrolytes on PVDF Layer-by-layer assembly DCMD [137]
wetting
Surface coating and layer-by- Improved anti-wetting against cationic
Polyphenols and polyelectrolytes on PVDF susbstrate DCMD [143]
layer assembly surfactant fpr treatment of saline wastewater
Crosslinked PVDF outer layer and PVDF/PEG inner layer hollow 2 1
Spinning DCMD High flux of 96.7 kg m− h− [136]
fiber membrane

15
F.E. Ahmed et al. Desalination 517 (2021) 115183

Table 8
Comparison of emerging technologies for seawater in this review and reverse osmosis.
Technology Thermal energy Electrical energy Recovery Advantages Disadvantages TRL
consumption (kWh consumption (kWh (%)
m− 3) m− 3)

Reverse osmosis 0 2–5 30–50 • Well-established • Increasing feed salinity increases required 9
• No phase change: lower energy energy
consumption than thermal • Lack of suitable membrane materials for
desalination high temperature, high pressure
• High separation efficiency applications.
• Pretreatment needed
• Membrane fouling
Forward osmosis 0 3–8 – • Osmosis step requires less energy • Suitable membrane materialsSuitable draw 4
• Low propensity to fouling solution
• Low concentration polarization • Energy consumption of draw solution
recovery step
Membrane 100 1–3.65 60–80 • Low-grade waste heat can be used • Thermal polarization 5
distillation • Low temperature requirements • Low membrane flux
• No applied pressure • Suitable for renewable energy desalination
• Not limited by feed salinity
• High separation efficiency
Electrodialysis 0 3.6–6.6a,b,c – • Low fouling propensity • Only multi-stage ED shows potential for 4
• High water recovery seawater dsesalination
• Cost of ion exchange membranes
CDI 0 Not applicable to – • Low fouling propensity • Not suitable for seawater 4–5
seawater • Chemical-free • SEC more sensitive to feed salinity
• No applied pressure
Desalination <1 kWh [193,223]b,c 95 • Low fouling propensity • Lack of high capacity electrode materials –
battery • Chemical-free • Low salt rejection
• No applied pressure
a
For a lab-scale multi-stage ED system.
b
Further investigation needed to determine net energy consumption of scaled up desalination battery [193].
c
Only the desalting step is considered; pretreatment and post-treatment not taken into account.

Table 9 Table 10
Features of recent pilot-scale studies for FO, MD and ED desalination. Main aspects investigated in each emerging desalination technology between
Process Application Membrane Plant capacity Reference
2017 and 2021.
configuration Forward osmosis • Novel draw solutes
Membrane modification
10–10,000 m3/
•
Forward Seawater Flat sheet; [224,225]
• Pilot-scale FO systems
osmosis desalination; hollow fiber; day
• Fouling characterization
wastewater spiral wound
• Hybrid FO systems
treatment;
Membrane distillation • Special wettability membranes
brackish water
• Integrated heat recovery
desalination
Renewable energy MD
2–400 m3/day
•
Membrane Seawater Spiral wound; [226–228]
• Hybrid MD systems
distillation desalination; hollow fiber;
• Alternative heating techniques
RO brine flat sheet
Electrodialysis • Hybrid ED systems
treatment
• Multistage ED
Electrodialysis Brackish water Flat sheet 100–20,000 m3/ [229]
• Ion exchange membranes
desalination; day
• Zero liquid discharge
RO brine
Capacitive deionization • Electrode materials
treatment

operation, as energy storage devices remain expensive and inefficient.

[253]. Ali et al. point out that solar technologies that concentrate solar
heat, such as concentrating solar power (CSP), are suitable for FO and
MD, whereas PV and wind electricity has been more commonly applied
to RO and ED systems [251]. Several studies investigating the coupling
of solar energy [254–258] and geothermal energy [259–263] with MD
can also be found in literature, although reducing the high energy
consumption of these systems is considered an important direction in
furthering renewable powered MD. It is expected that improving the
energy efficiency of desalination systems and renewable energy tech­
nologies, as well as the optimization of hybrid renewable energy sys­
tems, will create more opportunities in renewable energy desalination.

Fig. 15. Hybrid-FO-MD module showing flow of draw solution (DS) and
distillate (D) [235].

16
F.E. Ahmed et al.
Fig. 16. Overview of renewable energy technologies with RO, FO, MD and ED [251].
5. Conclusion
Energy-efficient low cost desalination is critical for sustainable
development. Innovation in research is key to bringing emerging pro­
cesses to higher levels of technological maturity in order for them to
compete with conventional processes such as reverse osmosis and
multistage flash for seawater desalination, or for niche applications. Of
niche applications, brine treatment and zero liquid discharge are of
utmost importance as the volume of byproducts of desalination increase
with global desalination installation capacity. National desalination
initiatives and research programs in several countries have sought to
push the development of lab-scale and near-commercialization tech­
nologies, which we present in this review. We focus on three types of
desalination: forward osmosis, membrane distillation and electro­
chemical desalination. The two former technologies have several pilot
facilities and technology developers, but full-scale commercialization
still requires breakthroughs in overcoming operational challenges. The
third, while applied to brackish water desalination, remains limited by
lack of suitable materials and innovative concepts.
Nanoscience has revolutionized membrane research. Emerging
desalination technologies have particularly profited from the use of
nanomaterials. Novel membrane designs for FO incorporating nano­
materials in both the active and support layer have led to significant
performance enhancement in terms of flux, salt rejection and anti-
fouling ability. Fabrication techniques including electrospinning have
been widely investigated for fabricating TFC-FO support with unique
architectures, due to its versatility and the high porosity and inter­
connected porous structure of electrospun membranes. However,
membrane development is only one aspect of moving emerging desali­
nation technologies towards commercialization. The lack of low cost
methods to regenerate the draw solution presents a major hindrance in
the industrial implementation of FO. on the other hand, wettability has
been a key membrane parameter affecting long-term performance of MD
systems. Novel membrane materials exploit special wettability such as
superhydrophobic, omniphobic, hydrophilic-on-hydrophobic, hydro­
phobic-on-hydrophilic surfaces. Very recently, researchers have
ventured into exploring the performance of these membranes under
more realistic feed and operating conditions.
Energy consumption is also dependent on early and accurate process
monitoring and control. Focus on process monitoring and control using
non-invasive in situ techniques can potentially reduce costs associated
with manual sampling, enable early detection, increase membrane life
and reduce frequency of membrane replacement by encouraging pre­
ventive maintenance. In both MD and FO, development of electrical and
optical tools opens new doors for incorporating real-time monitoring
into MD systems. While membrane development remains the most
17
Desalination 517 (2021) 115183
important aspect investigated by researchers, there has been increasing
interest in process improvement strategies in the last five years, focusing
on smart monitoring, hybrid systems and energy recovery.
Capacitive deionization is still considered an emerging technology
due to the low salt capacity of carbon-based materials that have been
used to date. However, new generation CDI, or desalination batteries,
incorporate battery materials to enhance salt capacity to previously
unattainable levels due to chemical bonding for storage of Na+ or Cl−
ions within the electrode material, as opposed to on the surface only.
Developments in this area present an exciting avenue for further
research which would include the investigation of different material
architectures and potential for upscaling.
Based on literature surveyed in this review, we make recommenda­
tions to guide future research and development to realize full-scale
commercial applications for each of the aforementioned technologies
in the near future:
• Although high flux, high salt rejection membranes are sought for FO
desalination, it is likely that transition from pilot scale to full scale
facilities will only take place when low-cost methods for draw so­
lution recovery are developed. Further studies in hybrid FO system
design are thus a logical direction for research in forward osmosis to
drive FO desalination towards lower costs.
• Carbon nanomaterials have been incorporated in FO membranes for
enhanced performance, but pilot-scale studies of these membranes
are non-existent.
• In MD, special wettability materials, especially superhydrophobic
and dual layer membranes are promising for flux enhancement and
long-term wetting resistance. However, feed composition and oper­
ating conditions may drastically alter the performance of these
membranes. Depending on the feed composition, membranes with
modified wettability that may be exhibit enhanced performance for
treating simple aqueous NaCl solutions tested in the lab may not
perform under real testing conditions and complex feed solutions. In
fact, there is evidence that a modified dual layer membrane may
encourage undesirable scale formation. More studies are needed to
study the effect of modification on membrane performance and
stability under real testing conditions. At a fundamental level, this
prompts a deeper understanding of membrane-feed interactions,
especially at elevated temperatures. On a practical level, the effect of
modified wettability, membrane design and configuration, system
size must be investigated with respect to wetting, scale formation
and fouling behavior with real feed solutions.
• For MD and FO, both of which have multiple pilot-scale facilities,
system design and engineering effects of upscaling should be given as
much attention as, if not more than, membrane development.
F.E. Ahmed et al.
• As new tools for in situ process monitoring and control are being
developed, attention must also be paid to the efficient incorporation
of these tools in terms of system design, as well as their potential for
upscaling. Such tools may be more easily incorporated in emerging
technologies that have not yet fully reached commercial scale where
there is greater potential for new designs and modifications.
• Research in the area of desalination battery is still in its infancy and
is likely to be driven by development of new materials, particularly
battery electrodes whose properties may have to be altered for use as
underwater electrodes.
• More studies, especially on the pilot-scale, are needed to explore the
commercial applicability and scalability of hybrid systems involving
emerging desalination technologies with respect to energy con­
sumption, product water quality, water recovery and resource
recovery.
Declaration of competing interest
The authors of this manuscript declare that there is no conflict of
interest.
Acknowledgments
The authors would like to acknowledge the support of NYU Abu
Dhabi for funding this work.
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