Desalination 391 (2016) 43–60

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Desalination

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

Recent trends in membranes and membrane processes for desalination

P.S. Goh a, T. Matsuura b,⁎, A.F. Ismail a,⁎, N. Hilal c,d
a
Advanced Membrane Technology Research Centre, Universiti Teknologi Malaysia, 81310, Johor, Malaysia
b
Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur Private, Ottawa, Ontario, K1N 6N5, Canada
c
Centre for Water Advanced Technologies and Environmental Research (CWATER), College of Engineering, Swansea University, Singleton Park, Swansea SA2 8PP, UK
d
Qatar Energy and Environment Research Institute (QEERI), Doha, State of Qatar

H I G H L I G H T S

• Current trends of membrane materials for desalination

• Emerging membrane-based desalination processes
• Challenges and future outlook of novel membranes and membrane processes

a r t i c l e i n f o a b s t r a c t

Article history: Access to clean water resource continues to be the most urgent and pressing global issue where hiking economic
Received 14 October 2015 and ecological needs have urged for more water-efficient technologies. Membrane-based separations for desali-
Received in revised form 15 December 2015 nation are playing an increasingly important role to provide adequate water resources of desirable quality for a
Accepted 20 December 2015
wide spectrum of designated applications. The engagement of multidisciplinary research areas into the commer-
Available online 4 January 2016
cial membrane and membrane systems offers an opportunity to refine and optimise current techniques as well as
Keywords:
provides new insight and novel methods of purifying water. The advancement of material science and engineer-
Membranes ing reveals the potentials to solve real-world practical problems and heighten the current technologies. This re-
Membrane processes view highlights some of the latest notable achievements of novel advanced membrane materials and emerging
Desalination membrane processes for water solution. The unique characteristics of advanced membranes and emerging mem-
brane processes in leading the state-of-the-art desalination are presented. Lastly, the future directions for re-
search, development and commercialization of membrane and membrane processes are critically discussed. It
is expected that, the promising and well-adapted characteristics possessed by the novel membranes and ad-
vanced membrane processes can provide meaningful inspiration for breakthrough technologies and solutions
where soon they will be translated into exploitable innovations in industries.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction safe drinking water, waste water treatment is considered a promising

The burgeoning population growth, urbanization and industrializa-
tion have increased the demands for reliable water resources. The
effects of weather change, which is also closely tied to the rapid growth,
have further complicated and exacerbated the balance between water
supply and demand. With this joint pressure, the issues linked to
water stress and shortage are expected to be widespread and increase
significantly for the years to come. The growing awareness towards
the far-reaching impacts of water scarcity and declining water quality
on the environment and mankind has pushed considerable efforts of
searching sustainable solutions to counter the on-going global chal-
lenge. Among the many strategies adopted to provide affordable and
⁎ Corresponding authors.
E-mail addresses: matsuura@uottawa.ca (T. Matsuura), fauzi.ismail@gmail.com
(A.F. Ismail).
solution to meet the ever rising demand and alleviate the alarming
problems [1,2].
Undoubtedly, desalination and wastewater treatment have
provided valuable opportunity to avoid the complete depletion and
diminishment of fresh water resources. Particularly, desalination has
been recognised as the essential contributor to reduce water stress in
coastal and inland regions through the production of fresh water from
seawater, saline groundwater, drainage water and treated wastewater.
Desalination and wastewater treatment based on membrane technolo-
gy is one of the approaches which has been extensively explored to
tackle the challenge of increasing access to clean drinking water in
order to sustain the rapidly growing global population as well as to
ensure economic progress. The research and industrial community has
been thinking strategically and looking beyond the fence line to fully
utilize membrane technology as cost-effective candidate to an
expanding range of purification and separation needs such as water

http://dx.doi.org/10.1016/j.desal.2015.12.016
0011-9164/© 2015 Elsevier B.V. All rights reserved.
44 P.S. Goh et al. / Desalination 391 (2016) 43–60
and wastewater treatment, brackish and seawater desalination. In fact,
recent progresses have witnessed the potential and reliability of apply-
ing commercially available membranes and membrane systems to re-
lieve water issues [3,4]. Pressure-driven membrane technologies such
as reverse osmosis (RO) have long gained great global interest to offer
affordable yet effective solutions to achieve promising product water
quality while imposing a smaller footprint of water treatment plant.
Generally, membranes dedicated for desalination are designed and
formulated to achieve high throughput and selectivity while exhibiting
high mechanical integrity and resistance towards fouling at the mini-
mum processing costs [5]. However, the development of membrane
that can one size fit all at commercially interesting level remains a
great challenge. Typically, the membrane separation efficiency is
primarily impeded by two physical limitations, i.e. i) concentration
polarisation which is caused by the increased concentration at the mem-
brane surface resulted from selective transfer of some species under the
effect of transmembrane driving forces and ii) membrane fouling which
is strongly related to factors such as solution chemistry, level of pre-
treatment, membrane properties and operating conditions [6]. Addition-
ally, commercially available polymeric membranes for water separation
are still suffering from several drawbacks and challenges including the
trade-off relationship between productivity and selectivity [4]. Normally,
membrane fouling represents a greater and complex problem which can
detrimentally deteriorate membrane lifespan, hence poses a serious
threat to the application and popularity of membrane separation tech-
nology [7]. The irreversible organic and biological fouling of a membrane,
which inevitably results in the permanent loss of the membrane's per-
meate flux, has prompted numerous contemporary investigations to en-
hance the membrane's anti-fouling properties through membrane
formulations or surface modifications [8–10].Considering the adverse
impacts of membrane fouling, approaches for fouling mitigation have
been arousing great research efforts. Furthermore, research has also
been actively pursued to resolve the trade-off issue. As part of the solu-
tions, new membrane materials have been developed to tailor and opti-
mize the parameters which are known to influence the fouling
mechanism and propensity [11]. Enhanced membrane properties in
terms of their pore size and pore size distribution as well as the surface
charge, hydrophilicity and roughness are fine-tuned through the innova-
tive and multidisciplinary efforts adopted from the holistic interplay
between membrane engineering and other emerging fields such as ad-
vanced materials and nanotechnology.
Nano-engineered materials have found numerous applications
that can potentially improve the existing technologies. Owing to their
special properties relative to bulk material, the introduction of
nanomaterials and nanotechnology in the field of membrane-based
water and waste water treatment has been a hot topic of research and
development in the past decade, and is likely to continue to be for a
long time [12,13]. While the existing technology for water treatment
is suffering from the inherent limitations, the emerging nanotechnology
provides a versatile platform to furnish affordable and safe drinking
water to address global water shortage issues. With the advancement
that involves cross disciplinary science and engineering subjects,
nanotechnology can favourably render a variety of options to tailor-
make solutions through different top-down or bottom-up approaches
to tackle a wide range of conventional and emerging pollutants such
as heavy metals, biological toxins, organic and inorganic solutes, just
to name a few. Mounting evidences from the past studies have indicated
that this new material revolution poses profound impact on heighten-
ing the membrane-based separation performance.
Despite the outstanding achievement made by the commercially
available membrane technologies, research continues to seek for more
rooms of improvements in terms of water cost, particularly the energy
consumption and recovery which are directly associated to the unit
water cost. For instance, regardless the efforts made, the average energy
consumption for seawater desalination using RO is still higher than that
of theoretical energy required. Thus, based on this reason, there is a
substantial need to call for innovative membrane processes and tech-
nologies to improve the current water treatment systems. Currently, os-
motically driven membrane processes (ODMPs) which are endowed
with energy-saving features for water purification and clean renewable
energy technologies have emerged as one of the most prominent and
fast-moving researches in its field [6]. Recently, forward osmosis (FO)
and pressure retarded osmosis (PRO) have been addressed as remark-
able and revolutionary ODMPs for power generation, desalination and
wastewater treatment. The key advantages of ODMPs over the pressure
driven membrane processes are their low energy consumption, low
fouling propensity hence minimum cleaning, high salt rejection and
high water flux [14]. On the other hand, owing to their several unique
characteristics such as total rejection for ultrapure water production, in-
sensitivity to feed concentration and stable performance at high con-
taminant concentrations, thermally driven membrane distillation
(MD) has gained equally important attentions as one of the most highly
researched membrane-based separation processes to overcome the
limitations at the conditions where those conventional processes can-
not practically operate [15,16]. It is worth mentioning that, membrane
capacitive deionisation (MCDI) has also been prominently explored to
overcome some limitations of the conventional CDI desalination
process. However, due to some inherent bottlenecks such as extensive
energy consumption in thermally driven separation and the challenge
to operate FO alone for a municipal scale application at the current
stage, the stand alone separation processes with a single step could
not match the actual challenges [17]. By considering the pluses and
minuses of these systems, integrated membrane system allows more ef-
ficient processes as the strength and advantages of each system can be
optimally harnessed and exploited [18,19].
This review focuses on the recent development of novel membranes
and membrane processes for desalination. The modification approaches
of membrane materials through the incorporation of advanced
materials, particularly nanomaterials, as well as surface modification
are presented. In the second part of this review, the basic features and
applications of some emerging membrane-based separation technolo-
gies namely FO, PRO, MD and MCDI as well as their roles in the integrat-
ed membrane system are briefly overviewed. Subsequently, the
challenges and future outlook of novel membranes and membrane sys-
tems for desalination and wastewater treatment are critically discussed.
Obviously, tremendous research efforts have been dedicated towards
understanding the dynamics of novel membrane materials and ad-
vanced membrane-based separation processes. With the ongoing re-
search, it is possible that more advancements and more conclusive
findings can be noted in the years ahead, especially in view of economic
and environmental sustainability [20].
2. Novel advanced membrane for desalination
Thanks to the ceaseless advances made in science and technology, a
wide range of polymers and production techniques have been used in a
great diversity of separation membranes which were tailored for an ef-
fective desalination process [21,22].The ultimate performance of a
desalination membrane is intimately dependant on the materials they
are made from in which the composition of the membrane plays a key
role to determine the important properties such as salt rejection, fouling
propensity, mechanical strength, and reactivity. Commercially, thin film
composite (TFC) polyamide (PA) and cellulose acetate (CA) membranes
have been widely used for RO and FO whereas hydrophobic
polytetrafluoroethylene (PTFE) and polyvinylidene-fluoride (PVDF)
have been commonly used in MD [20]. Despite the efforts made for
the selection of the best membrane materials and their preparation
technique based on the objective and requirement of the process, they
may not suffice to reach the best performance. It is due to the fact that
the inherent properties of the used materials may have adverse effect
on the separation [23]. Typically, selectivity-flux trade off exists as an in-
herent problem for all polymeric membranes, owing to the intrinsically
 P.S. Goh et al. / Desalination 391 (2016) 43–60 45

contradicting effects between the polymer chain stiffness and inter-
chain spacing [24,25]. Besides that, due to the destructive effects of
membrane fouling, different strategies have been established to en-
hance the fouling resistance of desalination membranes, particularly
that for pressure-driven processes, in order to lower the energy usage,
enhance process reliability and minimize the environmental impact of
sea-water desalination [26].The findings from numerous investigations
evidently showed that the membrane fouling resistance can be
improved by smoothing membrane surface, increasing surface hydro-
philicity and introducing strong electrostatic repulsion between
membrane surface and charged foulants [27,28].The development of
anti-biofouling membrane with smooth, hydrophilic surfaces has
shown resistance to the adhesion of protein and bacteria, hence suc-
cessfully reduced the use of cleaning protocols and biocides in water
treatment process.
Since membranes that are intrinsically incorporated with advanced
functionalities to resolve the above-mentioned issues are uncommon,
modification of membrane through the incorporation of additive with de-
sired functionalities or the surface modification of membrane is necessary
to achieve the goal. In brief, the current common goal of membrane mod-
ification is to render enhanced membrane properties, particularly in
terms of product water quality, permeability and antifouling properties,
through facile and straightforward methods that feature the ease of syn-
thesis, reproducibility and most importantly, high potential to be up-
scaled or mass-produced for practical application. This section presents
the recent progresses made in the development of novel advanced mem-
brane through the fabrication of nanocomposite membrane and modifi-
cation of membrane surface to cater for the desired properties of
membranes for desalination. Table 1 summarizes the current trend in
polymeric membranes for desalination [29–55]. Certainly, the application
and progress of these novel membranes in water treatment further affirm
scientists' commitment by clearly articulating the possibility of resolving
water-related issues with the heightened membrane performance.
2.1. Nanocomposite membrane
A significant number of studies on nano-enhanced membranes have
focused on the introduction of nanomaterials into polymeric mem-
branes. In general, when they are incorporated into membrane,
nanomaterials open doors to new properties that macroscale materials
do not share. It is expected that more emerging new contaminants can
be treated effectively even at low concentrations, due to the increased
specificity of nanotechnology and the development of smart membrane
tailored for specific uses to render novel reactions at the nanoscale with
the increased number of surface atoms. Generally, two approaches have
been utilized to introduce nanomaterials as additive in the polymer ma-
trix i.e. i) incorporation of the nanomaterials during the formation of
dope and ii) coating of nanoparticles on the surface of membrane via
chemical bonding or self-assembly [23].The different characteristics
with desired purposes can be invoked through the interaction between
the nanomaterials surface and polymeric chains and/or solvent during
the membrane fabrication process. It is also well accepted that the type
and the size of nanoparticles as well as their concentration in the dope
are of great importance in the membrane morphology and permeability
[23,56]. Nanomaterials that hold potentials to create synergism or multi-
function when integrated into the polymer system are metal/metal
oxide nanoparticles, carbon based nanomaterials and biomimetic
aquaporin (AQP).
he incorporation of a wide range of metal/metal oxide nanoparticles
into the polymeric membranes has been the focus of numerous investi-
gations since last decade [57]. The nanoparticles which are commonly
reported in desalination membrane fabrication are titanium dioxide
(TiO2), zeolites, silica and silver. Among the metal/metal oxides' host
of remarkable traits, some of the useful ones for desalination include an-
timicrobial, super-hydrophilic and photocatalytic properties. Silver
nanoparticles are well known as antibacterial materials based on its in-
teraction with sulfur and phosphorous to further damage bacterial pro-
teins, which allows effective mitigation of biofouling when they are
incorporated in the membrane. On the other hand, due to the attractive
super-hydrophilicity and photocatalytic properties, the addition of TiO2
nanoparticles can not only improve the hydrophilicity but also alleviate
the biofouling problem [58]. Fullerene-based nanomaterials such as car-
bon nanotubes (CNTs) and graphene-based nanomaterials are emerg-
ing as versatile new materials with properties that suggest a great
potential for improving water treatment technologies, particularly in
membrane separation. Fullerene nanomaterials are intrinsically
endowed with some exciting properties in terms of their mechanical
strength, ability to tailor size, flexibility in modifying functionality, and

Table 1
Current trend in polymeric membranes for desalination.

Membrane configurations Material description Operating mode Reference

Asymmetric flat sheet/hollow fiber membranes Cellulose acetate (CA) and cellulose triacetate (CTA) membrane through phase inversion RO, ODMP [29,30]
Flat sheet/hollow fiber mixed matrix membranes Incorporation of nanomaterials into CA and CTA, membrane formation through phase RO, ODMP [31–34]
inversion
Polyamide-based TFC Nanofillers: silica, carbon nanotubes, silver RO, ODMP [35,36]
Active layer-PA from Interfacial polymerization (eg. m-phenylenediamine (MPD) and
trimesoyl chloride (TMC))
Substrate- porous UF/NF (PSf, PES, PAN) flat sheet membrane
Active layer-PA from Interfacial polymerization RO, ODMP [37,38]
Substrate- electrospun nanofiber (polyvinylidene fluoride (PVDF),polyvinyl alcohol (PVA))
as substrate
Polyelectrolyte-based TFC Active layer- layer-by-layer deposition of polyelectrolytes (Poly(styrene sulfonate), RO, ODMP [39]
Poly(allylamine hydrochloride))
Polyamide-based TFN Active layer-PA from Interfacial polymerization incorporated with nanofillers RO, ODMP [40–44]
Substrate- porous UF/NF (PSf, PES) flat sheet membrane
Active layer-PA from Interfacial polymerization RO, ODMP [45,46]
Substrate- porous UF/NF (PSf, PES) flat sheet membrane incorporated with nanofillers
Flat sheet/hollow fiber porous hydrophobic Nanofillers: silica, graphene oxide, titania nanotube MD [47–49]
membranes
PTFE, polyethylene (PE), PES and PVDF
Porous hydrophobic mixed matrix membranes Incorporation of nanomaterials into hydrophobic, membrane formation through phase MD [50–52]
inversion

Nanofillers: carbon nanotubes, nanodiamond, clay

Ion exchange membrane Anion exchange membrane: aminated PSf, aminated PVDF MCDI [53–55]

Cation exchange membrane: sulfonated polyphenylene (PP) oxide

46 P.S. Goh et al. / Desalination 391 (2016) 43–60
electron affinity that enables the profound contributions of their poten-
tials for new membrane-based desalination technologies [59].The
hydrophobic surface in the interior of a defect-free carbon-based
nanomaterials also allow for a nearly frictionless flow [60]. Simulta-
neously, the membrane surface hydrophilicity and roughness can also
be tailored through the attachment of modified carbon-based materials
such as functionalized CNTs and graphene oxide (GO) [61]. One of the
important structural properties that merits CNTs as a favourable
nanomaterial for desalination is their ability to reject dissolved ions
while enabling water molecules to pass through [20,62].The small and
controllable diameter of CNTs allows the design of desalination mem-
brane in a fashion where fluid can selectively flow through the hollow
core of the CNT. Graphene-based nanomaterials have shown potential
application for making an ultra-fast, energy-efficient and environmen-
tally friendly generation of desalination membrane [60,63]. Numerous
computational studies have predicted that nanoporous graphene
could outperform the commercial water desalination membrane
where it can work under lower pressures and provide well-defined
channels that can filter salty water at a faster rate than RO membranes
[64]. Graphene sheets perforated with micropores have been proposed
as a potential star to allow ultrafast separation of atomic species where
water molecules may permeate between graphene sheets across the
polymeric matrix [65,66].
Over the last five years, the participation of aquaporin-based mem-
branes in desalination technology has opened up an exciting direction
in desalination due to the high AQP water transport and excellent selec-
tivity. Biomimetic AQP membranes represent a rapid moving field
where the main attractions of AQP relevant for biomimetic membrane
technology for water purification are i) highly permeable, ii) highly se-
lective, iii) defect free (iv) mechanically stable to withstand the required
pressure for target applications, (v) chemically and biologically stable
for long term use, and (v) easy to scale up at reasonable cost [67,
68].The pioneering work conducted by Kumar et al. [69] indicated that
AQP-incorporated triblock copolymer membranes could lead to more
controllable, productive and sustainable water treatment membranes.
Following that, systematic researches have been conducted on active
AQP based composite membranes, which exhibited competitive water
permeability and enhanced ion rejections for existing RO, FO or NF sys-
tem [70–72]. Several approaches for fabricating AQP-based composite
membranes with compatible NaCl rejection have been reported [73,74].
2.1.1. Thin film nanocomposite
Over the last 30 years, TFC, which is generally synthesized through
interfacial polymerization between m-phenylenediamine (MPD) and
trimesoyl chloride (TMC) on a porous substrate layer, remains as the
primary choice for the state-of-the-art RO desalination processes [27].
Although TFC membrane has demonstrated promising characteristics
to produce very pure water from highly contaminated sources with
good water flux and salt rejection as well as good mechanical strength
and tolerance to a wide range of feed pH [75], the hydrophobic aromatic
groups and high cross-linking degree at the selective layer have inher-
ently limited water flux. This type of membrane is also found to be high-
ly susceptible towards fouling, which ultimately increases the energy
consumption and desalination cost. Recently, several routes to increase
water permeability and anti-fouling properties without compromising
selectivity have been proposed to architecturally modify the chemistry
or morphology of the active layer of TFC membranes. One of the new ap-
proaches was implemented through the integration of functional nano-
particles with super-hydrophilicity and anti-microbial properties
within the polymer films, which has led to the creation of an emerging
class of thin film nanocomposite (TFN) RO membranes. The continual
studies have revealed that while TFN membrane can purify water as
well as TFC membranes, it is value-added with some significantly im-
proved properties in which the inorganic additives have contributed
not only to the improvement of diffusion features of the formed
membrane but also to the enhancement of the degree of hydrophilicity
and hence its fouling resistance. The inorganic nanomaterials are found
to improve film formation by offering the following benefits:
i) increasing the diffusion rate of monomers to the interface
ii) expanding the wet zone on the top of support layer and iii) capturing
by products and controlling reaction pH (buffer agent) [41,76,77].
AquaporinZ-containing proteoliposomes were added to the MPD aque-
ous solution, followed by the reaction with TMC in the organic phase to
form a salt-rejection PA layer via interfacial polymerization [73]. When
benchmarked against commercial RO membranes, it is found that the
high performance biomimetic membranes show a comparable NaCl re-
jection and an order of magnitude higher flux than the seawater RO
membrane SW30HR. Due to the ease of TFC fabrication, the resulting
membrane has an area greater than 200 cm2 which can be easily scaled
up to produce membrane areas at an industrial scale. Furthermore, the
PA layer may also serve as a protection layer to the proteoliposomes
against environmental factors and provide a mechanical support to
them. This leads to high mechanical stability of membranes, which is
an important requirement for desalination applications. Hollow fiber
TFN membrane embedded with AQP-incorporated proteoliposomes
has been recently studied for their FO separation performance [78]. As
depicted in Fig. 1, a new protocol has been established where the vesi-
cles with AQPs are immobilized on the hollow fiber polyethersulfone
substrate and subsequently coated by a layer of PA to cover or connect
these vesicles through interfacial polymerization. The defect free PA
layer immobilised with AQP could effectively function as a selective
layer, which determines the water permeability and salt rejection. It
was found that, The biomimetic membrane with a high AQP covering
density exhibited a 40 L m−2 h−1 permeate flux at 5 bar, almost 200%
as much as the flux of a typical commercial BW30 RO membrane, and
rejection of 97.5% to a 500 ppm NaCl solution, which outperformed
the commercial membrane tested under the same conditions.
Due to the different roles played by the PA selective thin layer and
porous substrate, the incorporation of nanomaterials in these layers
may impart different impacts to the separation properties. The effects
of the incorporation of Zeolite A in PA selective layer and polysulfone
(PSf) substrate have been investigated [79]. Overall, it was found that
regardless of the position of nanoparticles, the resultant TFN exhibited
smoother and more hydrophilic surface, higher water permeability
and salt rejection as well as greater resistance to physical compaction.
However, the incorporation of zeolites in the substrate could resist
physical compaction better via enhanced mechanical stability mean-
while the embedment of zeolites A in the selective layer resisted com-
paction by mitigating densification of polymer film. NaY zeolite
nanoparticles have also been embedded into the PA layer via interfacial
polymerization to form a novel zeolite–PA TFN membrane [44].Owing
to the hydrophilicity of NaY zeolite, the orientated distribution of the
nanoparticles at the bottom of the PA thin layer on the PSf side, instead
of the PA surface side, allowed the nanoparticles to play a greater role in
heightening the membrane separation performance. Under the opti-
mum conditions of 0.15 wt% NaY zeolite, the water flux increased
from 0.95 to 1.78 m3/m2/day with the incorporation of the zeolite nano-
particles, while providing a high salt rejection of 98.8%. TiO2 has also
been used to structurally modify the PSf substrate of FO TFN membrane
[80]. Compared to the control TFC membrane, the FO water flux of TFN
was reported to increase significantly from 4.2 to 8.1 L/m2.h and from
6.9 to 13.8 L/m2 h (AL-DS orientation), respectively, when seawater
was used as feed solution and 2 M NaCl was used as draw solution.
The increase in water flux can be attributed to the formation of finger-
like macrovoids that connect the top and bottom layer of the substrate
and reduce the tortuosity, consequently decrease the internal concen-
tration polarisation effect.
During a typical desalination treatment, the biofouling of RO mem-
branes is resolved through the addition of free chlorine during the pre-
treatment of feed solution. Despite the dechlorination stage prior to the
RO system, a minimum amount of free chlorine is intentionally left to
prevent the growth of the microorganisms. Unfortunately, the chemical
 P.S. Goh et al. / Desalination 391 (2016) 43–60 47

Fig. 1. The preparation of AQP hollow fiber membrane through the formation of polyamide layer to cover the AQP through interfacial polymerization [78].

interactions of aromatic polyamide with residual chlorine oxidant can
degrade the polyamide layer and subsequently deteriorate the perfor-
mance of the TFC membrane. Very recently, the hybrid of reduced
graphene oxide (rGO)/TiO2 has been embedded in the PA layer aimed
to enhance chlorine resistance and antifouling property, hence improve
the overall RO performance of the TFN [43]. At an optimum loading of
0.02 wt%, it was found that water flux was improved by 21% compared
to the TFC counterpart meanwhile the salt rejection of 99.45% was
achieved. In this hybrid system, rGO sheet served as a platform to re-
strict the aggregation of TiO2. As such, the well dispersed TiO2 could ef-
fectively render chlorine resistance and antifouling property and also
improve the separation performance of resulted membrane. TFC mem-
branes have also been modified with antimicrobial nanomaterials to in-
crease the antimicrobial activity and improve the biofouling resistance
of the resultant TFN. GO is one of the promising nanofillers to render an-
timicrobial properties while potentially increasing the TFN's permeabil-
ity and mechanical strength [81,82]. In a recent work, GO nanosheets
were covalently bound to the polyamide active layer to promote effi-
cient bacterial cell inactivation in which the number of viable E. coli
cells was reduced by 64.5% after contact with the TFN for 1 h, without
affecting the intrinsic transport properties of the TFN membrane for
desalination (Fig. 2). [83].
2.1.2. Mixed matrix membrane
Mixed matrix membranes (MMMs), which have been fabricated
through the direct incorporation of inorganic fillers into polymeric
host matrix, have been widely used as an alternative approach to
achieve synergetic effects between the nanofillers and host polymer
matrix. Compared to TFN, MMMs enjoy the ease of fabrication as the
nanofillers are typically added to the polymer dope, followed by phase
inversion technique to produce the flat sheet or hollow fiber MMMs.
CA/polyethylene glycol (PEG) RO membrane embedded with fused sil-
ica particles (FSP) has been reported [34]. The optimum performance
of desalination process was shown by 30 wt.% FSP in which the

Fig. 2. (a) GO nanosheets were covalently bound to the polyamide active, b) SEM images showed that the TFN promote efficient bacterial cell inactivation of E. coli cells after 1 h contact
time [83].
48 P.S. Goh et al. / Desalination 391 (2016) 43–60
permeation flux of 0.66 L/m2h and salt rejection of 98.4% were obtained.
The increase of permeation flux was mainly due to hydrophilic nature of
FSP in which the doping of FSP changed the permeate mobility and also
the polymer chain segmental motion and subsequently increased the
free volume of the MMMs. On the other hand, the electrostatic interac-
tions between the FSP and dense membrane prevented the formation of
undesired voids hence increased the salt rejection.
Denotation nanodiamond (DND) is a new generation of carbon-
based nanomaterial that has potential to enhance conventional hydro-
phobic membranes for water vapor flux in MD process [52]. Since the
outer core of the DNDs is graphitic and quite hydrophobic, they de-
crease pore wetting while enhancing the transport of pure water
vapor. As such, the incorporation of DNDs has favorably altered the
water–membrane interactions to enhance vapor permeability while
preventing liquid penetration into the membrane pores. Additionally,
the DNDs possess a graphitic ring structure with additional -COOH
and -OH groups on its surface which leads to specific interactions with
the water vapor molecules further leading to enhanced flux as shown
in the illustration in Fig. 3. As a result, the desalination performance
was consistently higher compared to that of PVDF in which maximum
permeate flux of 13.8 L/m2h and salt reduction of 99.9% could be
achieved. The structural, mechanical, interfacial, and separation charac-
teristics of the nanocomposite membranes have been historically asso-
ciated with the types of nanoparticles and their size as well as the
interaction of the nanoparticles with the host polymer and solvent dur-
ing the dope preparation. Particularly, the degree of dispersion of
nanomaterials in polymer matrix showed great impacts on the mechan-
ical strength of composite membrane performances [84].
Improving the compatibility of CNTs with polymer membrane ma-
trix through CNTs functionalization is a straight forward approach to
prevent the leakage of CNTs from the resultant nanocomposite mem-
brane in order to preserve the membrane tensile strength and minimize
CNTs loss into the environment from economic and environmental
points of view. The incorporation of dodecylamine (DDA) functional-
ized multiwalled carbon nanotubes (MWCNTs) in PSf membrane has
been attempted for the mitigation of membrane biofouling [85]. The
Fig. 3. The mechanism that takes place at the DND immobilized membranes. The enhanced flux is mainly attributed to the enhance hydrophilicity and interaction of water molecules with
functional groups on DND [52].
amide functionalized MWCNTs facilitated the dispersion of nanotubes
in the casting solutions and improved the interfacial compatibility and
stability of composite membranes. Owing to the antimicrobial proper-
ties rendered by the DDA/MWCNTs, the composite membrane embed-
ded with 0.5 wt.% of MWCNTs exhibited the highest flux recovery
(83%) and lowest total flux loss (29%) with reduced irreversible fouling
resistance (17%). Due to its capability to render hydrophilicity, mechan-
ical strength, chemical stability, ion exchange capacity and conductivity,
rGO has been incorporated into polyaniline (PANI) conductive anion ex-
change membranes for capacitive deionisation process [55]. The exper-
imental results indicated that the salt removing efficiency of membrane
assisted CDI was much higher than CDI without ion exchange mem-
branes. This feature was mainly attributed to the added rGO which
has helped to improve the dispersion of the PANI in the solvent to pro-
duce membrane with higher electrical conductivity and also high ion
exchange capacity.
2.2. Surface modified membrane
Surface modification that allows the structural engineering of poly-
meric membranes is performed to introduce abundant hydrophilic
functional groups onto the hydrophobic membranes by means of sever-
al well established approaches such as i) adsorption and surface coat-
ing; ii) chemical reactions induced by high energy substances (UV,
plasma) or oxidative treatment by strong acids and iii) surface grafting
of a functional monomer or polymer on a base membrane [8]. The
concept of surface hydrophilicity enhancement has been extended
to the surface modification of TFC. Hydrophilic additives such as
poly(m-aminostyrene-co-vinyl alcohol) and o-aminobenzoic acid–
triethylamine (o-ABA–TEA) salt have been introduced into the aqueous
phase during the interfacial polymerization of PA selective layer [27].
During the RO desalination process, these hydrophilic additives could
create an additional pathway to enhance water transport and provide
charge repulsion to increase salt rejection. As a result, the resultant
surface-modified membrane showed a considerable water flux increase
as well as lower flux decline. The antifouling mechanism of a
 P.S. Goh et al. / Desalination 391 (2016) 43–60
hydrophilic membrane surface can be attributed to the formation of a
compact hydration layer on the surface that may hinder the direct con-
tact of foulants with the membrane surfaces [86].
The introduction of zwitterionic polymers (ZPs) such as
polyphosphobetaine, polysulfonbetaine and polycarboxybetaine
which possess both anionic and cationic groups in a single monomer
unit onto the polyamide thin film represents an attractive alternative
to simultaneously enhance permeability and antifouling properties.
The intra- and inter- association between opposite charges of zwitterion
monomers facilitates the formation of “free water” hydration layers
which can be attributed to the ionic solvation of these “free water” mol-
ecules [87]. The strength of this hydration layer is thought to surpass the
hydrogen bonded water molecules in neutral hydrophilic polymers
[88].However, some studies also reasonably pointed out that, the high
surface free energy of hydrophilic membrane could induce the adhesion
strength of organic foulant, hence complicate the cleaning process,
therefore membrane with lower surface free energy may be more ben-
eficial in this aspects. One of the approaches to reduce the surface free
energy while maintaining the surface hydrophilicity is the modification
of membrane surface with surfactant that shows both hydrophilic and
oleophobic surface properties [8].
2.3. Graphene/graphene oxide membrane
While the development of nanocomposite and surface modified
membranes which consist of mainly polymeric materials is progressing
steadily towards practical applications, graphene membranes have also
attracted tremendous interest to elevate the performance of desalina-
tion membrane technology to offer significant improvement and energy
saving. Currently, several computational methods have been employed
to provide further insight of graphene membranes for desalination [89].
Several exciting computational work have outwardly shown that a
graphene membrane with sub-nanometer pores holds great potential
as desalination membrane when the channel pores are carefully tailored
to selectively control the passage of ions [90,91]. Also, being the thinnest
material, the two-dimensional sheets of graphene can be favourably
used as ultra-thin membranes to increase water flux [92]. The graphene
membranes which containing continuous channels allow the passage of
greater volume of water at the given pressure far lower than that of re-
quired by conventional polymeric membranes. While maintaining the
high salt rejection, single-sheet graphene membranes are 250 times
thinner than the selective layer in commercial RO membranes. As
such, a significant improvement in water flux of at least 250 times
could be expected under the same driving force [93]. The precisely con-
trolled pores can be custom formed on the graphene monolayers
through ion etching, self-assembly or doping. In order to tailor for
their desired applications, surface functionalities can also be introduced
through chemical modification such as oxidation and fluoridation. For
instance, the dangling bonds in the graphene pores can be saturated
with F atoms under a vacuum fluorine atmosphere [94].
One of the interesting feature of graphene when it is applied as FO
membrane is the exceptional strength of porous graphene which re-
quirement of a support layer can be ruled out. As such, when the exter-
nal hydraulic pressure is not necessary, the graphene FO membrane
exhibits nearly zero ICP [94]. It has been reported that for the FO system
using fluorinated porous graphene the water flux is about 1.8 × 104
times higher than that of a typical cellulose triacetate membrane.
While great efforts have been attempted to address the challenge to
achieve large-area, high quality and single-crystal graphene, free stand-
ing GO membrane has also opened a brand new era for assembling
membranes with enhanced ion selectivity performance due to their fac-
ile and large-scale production in solution. Moreover, the assembling of
GO thin film is much more feasible as GO can be readily dispersed to
form well-dispersed aqueous colloids in the absence of any surfactants
or stabilizing agents [95]. Recently, the tunability of water desalination
across graphene oxide framework (GOF) membranes, which consist of
49
layers of GO sheets covalently interconnected by linear boronic acid
linkers, has been reported [96]. Assessment using classical MD simula-
tions revealed that 100% salt rejection coupled to a water permeability
two orders of magnitude higher than any commercial RO membranes
can be achieved.
3. Emerging membrane processes
The application of RO process has rapidly bloomed since the 1960's
and has become the leading and preferred technology for seawater de-
salination by surpassing conventional thermal processes in many new
plant installations [97]. Currently, RO accounts for 60% of desalination
erections across the globe, thanks to its order of magnitude less energy
requirement than its thermal counterparts. Despite the unprecedented
success and significant growth of RO in desalination, it is also associated
with several severe drawbacks including relatively low water recovery
factors, scaling and biofouling, and high electrical energy cost, which
typically represents half of the total water production cost. [98].The
process limitations have eventually made RO less favourable for
energy-effective desalination as it presents a big challenge to make RO
desalination affordable for poorer countries [21,99,100]. Additionally,
higher energy consumption is also directly linked to a corresponding in-
crease in greenhouse gas emissions which further deteriorate the qual-
ity of the environment. Besides that, RO also suffers greatly from a high
rate of brine production in which current methods of brine disposal are
still inadequate to ensure sustainable management.
Research and commercial attentions in emerging ODMP, MD and
MCDI as illustrated in Fig. 4 are increasing globally due to the potential
of the processes to render significantly reduced operational cost with-
out sacrificing the desalination performance. The features and advances
include simple process design, minimal and reversible fouling due to
low or no hydraulic pressure application, as well as energy recovery
and reduction in energy consumption [101]. Albeit pressure driven
membrane processes are expected to maintain their leadership in the
near future, it is anticipated that emerging technologies such as FO,
PRO, MD and MCDI will soon find their values and places in the market
and industries. This section provides a brief overview on the features
and performance of the evolving FO, PRO, MD and MCDI processes by
comparing and contrasting with their counterpart RO process.
3.1. Forward osmosis
Research and development of FO have been actively carried out to
provide an alternative solution to the existing water problems through
desalination, power generation, food processing and wastewater treat-
ment. The exponentially increasing number of research papers and
comprehensive reviews published over the last few years has indicated
the increasing level of academic interest in this ODMP [14,102–108]. Re-
cently, the involvement of a few number of commercial companies,
such as Oasys Water Inc. and Hydration Technology Innovations (HTI)
Inc. through the investment of significant funding has implied the ea-
gerness of industry to exploit the technology to a greater extend. The
reason for the looming of FO in widespread application is primarily at-
tributed to its advantages over the conventionally available processes.
According to thermodynamic principles, FO process can occur sponta-
neously, hence it requires minimal energy input to achieve the separa-
tion. As FO does not operate with hydraulic pressure but with osmotic
pressure difference, when compared to traditional pressure-driven RO
membrane processes, FO has less membrane fouling, scaling, and
brine discharge. Moreover, the greenhouse gas emissions are consider-
ably less in compared to that of thermal techniques. Also, FO has the
prospect to effectively reduce the amount of rejected brine when high
osmotic pressure gradient is sufficiently maintained across the mem-
brane to help attain reasonable water flux and water recovery, hence
potentially reduces the environmental burden of brine disposal as
what typically is faced by many desalination plants, particularly for
50 P.S. Goh et al. / Desalination 391 (2016) 43–60
offshore desalination [109]. Another astonishing element of FO is that
when combined with industrial or power production processes that
produce waste heat, the electricity requirement is remarkably less
than for RO. Worth mentioning that, while RO membranes do not nec-
essarily provide good rejection for boron, which is usually in the form
of boric acid in the normal operating pH ranges, the re-circulating
draw solution dispenses an opportunity to improve boron rejection
which has long presented a challenge to the membrane industry.
In brief, FO process, similar to RO, requires a selectively permeable
membrane separating two fluids with different osmotic pressures to
participate in two major steps, i.e. the osmotic dilution of the draw solu-
tion and the generation of fresh water from the diluted draw solution
[109]. However, unlike those pressure-driven membrane processes,
FO only requires minimal external energy input for liquid circulation.
As such, a desalination plant operating on FO technology can be con-
structed at 90% of the construction cost and operated at 80% of the oper-
ation cost of an RO plant [110]. Nevertheless, when reconcentration
process for water recovery and draw solution reuse is concerned, an en-
ergy input is needed for the process [111,112]. In order to ensure the
Fig. 4. Schematic illustration of a) FO, b) PRO c) MD and d) MCDI (a–c: internet sources, d: [163]).
operation of FO plant on a continuous and economic basis, several sub-
stantial conditions must be fulfilled, i.e. i) appropriate selection of the
draw solution; ii) control of a constant osmotic pressure for the concen-
trated draw solution; iii) prevention of contamination of the draw solu-
tion with salts from the feed solution and back diffusion of the draw
solution to the feed solution and iv) robust FO membrane that can ade-
quately deal with flow on both sides. While the operating conditions
seem trivial to be solved, the properties hence capability of membrane
and draw solution are the two key factors that play crucial role in dictat-
ing the efficiency of the FO performance. Extensive efforts have been di-
rected to develop high performing FO membranes which can offer
better flux performance and also draw solutions with desired properties
in all aspects for FO applications [113]. With the availability of desired
membranes and draw solutions that are economically and technically
viable, it is expected that the construction and operating cost of FO
plants can be greatly reduced [110].
FO membranes are normally characterized with a thin rejection
layer and a support layer with high porosity and low tortuosity. Current-
ly, the CA and TFC FO membranes produced commercially are specially
 P.S. Goh et al. / Desalination 391 (2016) 43–60
Fig. 4 (continued).
designed to mitigate internal concentration polarization (ICP) by using
a much more open substrate than their RO counterpart [114,115]. Dur-
ing the fabrication of FO membranes, the polymer dope and membrane
formation conditions are manipulated to obtain finger-like macrovoid
structure so that the impact of ICP can be greatly reduced [116,35,
117].Similar to the RO counterpart, FO membranes can be moduled
into different common geometries such as spiral wound, flat sheet, tu-
bular or hollow fibre. Due to the absence of hydraulic pressure, FO is
less susceptible to severe fouling as the deposited layer is less
compacted. Unlike fouling in RO membranes, most of the organic and
inorganic foulants found on the FO membranes can be easily removed
by osmotic backwashing, hence the need for any chemical reagents for
cleaning is completely eliminated [118]. More than 98% water flux re-
covery could be obtained after water rinsing which is much higher
than that commonly observed in RO [6]. While research is devoted to
developing membranes feasible for FO, the search for suitable draw so-
lutions is also of great importance. In general, the draw solutes can be
broadly categorized into organic-based, inorganic-based and some
emerging draw solutions such as micellar solution, magnetic nanoparti-
cles (MNPs) and RO brines [109,119–122]. Typically, the primary
challenges associated with draw solutions are the availability of a suit-
able solution that is capable to provide strong driving force for mass
transport and the minimum energy consumption involved in the
51
reconcentration of the draw solution for continuous FO operation [6].
Precisely, a promising draw solution should exhibit high osmotic pres-
sure with minimum reverse diffusion and can be easily and economical-
ly reconcentrated and recovered. Most importantly the draw solution
must be of zero toxicity and should not degrade the membranes or
cause scaling or fouling on the membrane surface [123].
The sweet spots of FO process are unavoidably accompanied with
some practical challenges. One of the disadvantages of FO is a lower
quantity of freshwater per unit of water treated. The commercial poly-
meric membranes applied for pressure driven RO or NF system cannot
be suitably used for ODMP due to the presence of severe ICP within
the support layer. The new generation of FO membranes has overcome
this problem by reducing the thickness of the membrane support layer
which is thinner than conventional RO membrane [124–126]. As a
result, FO membrane is not tailored to tolerate high feed pressures. Con-
centration polarization on both sides of the asymmetric FO membrane,
i.e. ICP occurs within the membrane support layer and external concen-
tration polarization (ECP) exists at the membrane active layer surface,
should be responsible to the significant decrease of the effective trans-
membrane osmotic pressure which in turn serves as one of the major
factors that contribute to deteriorating water flux and recovery across
the membranes [127]. A debate has been raging recently where the
low energy and low cost feature of FO are seemingly too good to be
52 P.S. Goh et al. / Desalination 391 (2016) 43–60
true as significant amount of energy may still be required to regenerate
the draw solution. As a result, for seawater desalination, the energy re-
quirement of a standalone FO process is much higher than that of RO
[109]. Due to the concentration gradient nature of FO, the occurrence
of reverse solute flux across the membrane from the draw to the feed
solution is almost unavoidable. Recent researches have unfavourably
pointed out that the reverse solution diffusion of some multivalent
ions may expedite membrane fouling by interfering with the fouling
agents in the feed [128]. Furthermore, the lower solution diffusion coef-
ficients and larger ion sizes of multivalent ions also resulted in severe
ICP. Despite the limiting factors mentioned, in overall, the merits of FO
still outweigh its disadvantages. Therefore, if efficiently used, FO can
prove to be an efficient way of desalinating seawater [110]. Besides
that, FO hybrid systems can be used for the desalination of high-
salinity waters, which is not possible when using standalone RO process
[107].
3.2. Pressure retarded osmosis
PRO is an ODMP which possesses a great potential to provide sus-
tainable solutions for the burning needs of both clean water and green
energy. The osmotic power harvested by PRO represents a new class
of emerging renewable energy that is less periodic than other renew-
able sources like wind and solar energy [129,130]. In principle, PRO is
a method of producing renewable energy from the mixture of two
streams with different salinity. Typically, a simple PRO system takes in
surface water and seawater on either side of the membrane in which
permeate from a dilute feed stream enters a concentrated draw stream
in a pressurized state via osmosis. Through the pressure of draw-
permeate mixture, osmotic energy is converted into hydraulic energy
and the pressurized water which permeates through a PRO membrane
is used to drive a hydro-turbine for useful power extraction [131,132].
While exhibiting similar physical principles and process components
as FO, the key contribution of the unique PRO process is to facilitate con-
version of osmotic pressure difference to hydraulic pressure in order to
generate electricity when the hydraulic pressure is released through a
turbine or other devices. As it ought to be, the main application of PRO
is to generate power, rather than to perform separation [6]. The world's
first prototype osmotic power plant equipped with 2000 m2 of mem-
branes with marginal power output capacity between 2 kW and 4 kW
was opened by Statkraft in Norway. This potential source of energy is
capable to generate approximately 2000 TWh per year of electric
power to cater for approximately 10% of the current world energy de-
mand [133].The power company claims that the PRO energy cost can
be further brought down to an attractive level as the osmotic power
plant can be designed to operate at full capacity almost continuously.
Hence this technology can be cost competitive with other renewable
power sources such as wind power and biomass [134].
One of the profound challenges to meet the technical and economic
feasibility of PRO is the development of a PRO-specific membrane which
is yet to be commercially available. Structurally, PRO membrane is sim-
ilar to that of FO membrane in which the porous support layer in the
PRO membrane is thinner than that of the conventional RO membrane.
Additionally, excellent mechanical strength is one of the essential factor
to be considered in fabrication of the PRO membrane to withstand the
applied hydraulic pressure on the draw solution side of the membrane
[75,135]. It has been reported that the pressure applied can
unfavourably initiate membrane deformation thus lead to severe salt
leakage and reduce the power density [136]. As mentioned earlier, the
FO membrane is less prone to fouling on the feed side and even if it oc-
curs, it can be easily tackled with simple hydrodynamic cleaning
[137–139]. Whereas in PRO, as the membrane active layer is placed
against draw water, it was demonstrated that organic and inorganic
species in the feed water can easily deposit within the porous support
layer where hydrodynamic shear induced by cross-flow is absent. This
phenomenon is detrimental to the efficiency of PRO membrane
processes [136,140,141]. In recent years, the development of osmotic
membranes and membrane modules which can produce higher power
densities with PRO processes has been extensively investigated [114,
142–145]. So far, TFC membranes post-treated with ethanol or TFC
membrane subjected to NaOCl exposure [142] and solvent immersion
[146,147] have exhibited significant improvement in the water perme-
ability. Besides, in order to avoid heterogeneous compaction and un-
even deformation under a high pressure, membranes with sponge-like
structure are more favourable for PRO process for the advantages of
strong mechanical strength. Due to the large unsupported distance
over feed spacers, flat sheet PRO membranes tend to experience uncon-
trollable mechanical deformation [136]. Hence, attention has been
switched to the fabrication of hollow fiber membranes using polymer
with strong mechanical properties to enhance membrane mechanical
stability [148]. A recent study evidenced that an impressive power den-
sity of 20.9 W/m2 can be obtained by polyetherimide (PEI) hollow fiber
membranes when 1 mM NaCl and 1 M NaCl solution were used as feed
and draw solution, respectively [148].
3.3. Membrane distillation
MD, a third generation desalination technique, is a hybrid thermal-
membrane desalination process that utilises low-grade waste heat or
renewable energy and hydrophobic membrane to produce high quality
distillate [149].The main benefit of MD lies in the ability to operate at
lower hydrostatic pressure than conventional pressure-driven mem-
brane processes and a lower operating feed temperature compared to
conventional distillation [150]. As MD process can take place at normal
pressure and temperature lower than the boiling point of water, it could
be versatilely used to solve various wastewater problems. Over the last
decade, concerns on poor removal efficiency of small molecule contam-
inants and heavy metal ions have urged the research community and in-
dustries to seek for promising alternatives [151]. MD stands out as a
feasible option because it can provide higher removal efficiency for
these contaminants. For instance, MD demonstrated its excellent capa-
bility in the removal of boron contaminants with a rejection 99.8% and
almost complete rejections of heavy metals such as arsenic, chromium
or gold [151]. MD also emerges as a potential element to address the
issue of disposal of produced brine and extensive energy consumption,
which are the inherent drawbacks of conservative RO process, for the
sustainable growth of desalination technology [152]. Another strength
of this technology is that the high solute concentrations can be achieved
and ultrapure water can be produced in a single step. The world's first
seawater desalination plant based on MD was operated by Aquever in
2014 at Maldives. The plant has a capacity of 10,000 l of drinking
water per day and utilizes waste heat of a local power generator. Several
research projects also focused on the coupling of MD with solar energy
for seawater desalination and provided new insights into the large po-
tential for applications such as stand-alone desalination systems from
remote sites [153,154]. Due to the independency of trans-membrane
flux from feed concentration, MD holds the advantage of overcoming
the feed concentration limit of around 70,000 mg/L in conventional
RO plant, thus enables MD to serve as a compact low pressure operation
for further recovery of RO brines to reduce the significant cost associat-
ed to high discharge volumes particularly in inland groundwater
desalination system [155]. Recently, computational fluid dynamics sim-
ulations have been widely applied to study the transport phenomena
which include the momentum, heat and mass transfer in conventional
and newly designed MD modules in order to improve MD performance
[156].
MD is a breakthrough technology which combines membrane sepa-
ration and distillation, resulting in pure water production from seawater
using low-grade source of energy such as solar and geo-thermal energy
for a cost efficient, energy efficient liquid separation system. [152,157].
Principally, MD is a thermally driven membrane process which involves
transport of water vapor through microporous hydrophobic membrane
 P.S. Goh et al. / Desalination 391 (2016) 43–60
where the driving force of MD is supplied by the vapor pressure differ-
ence generated by temperature gradient imposed between the liquid/
vapor interfaces [150]. MD processes can be broadly classified into
four configurations, i.e. direct contact membrane distillation (DCMD),
air gap membrane distillation (AGMD), vacuum membrane distillation
(VMD) and sweep gas membrane distillation (SGMD), depending on
the methods to induce vapor pressure gradient across the membrane
and to collect the transported vapors from the permeate side. Out of
the four configurations, DCMDis the most favourable mode due to its
inherent simplicity without the need of external condensers [158]. Pre-
viously, the relatively slow progress and constraint in the commerciali-
zation of MD were related to i)the lack of commercially available high
performance membranes ii) high energy consumption with respect to
RO and iii) limited investigations carried out on module designing
[151]. However, owing to the recent and growing extensive research ac-
tivities carried out in various areas of MD, particularly the growing
availability of commercial hydrophobic membranes, the process has be-
come much more attractive due to the availability of better membranes
and the possibility to reap alternative energy sources [158]. Lately, the
evaluation of the practicability of MD seawater desalination has been
extended to pilot scale which focused on the harnessing of solar energy
either by photovoltaic panels or solar collectors with heat storage
mediums [149,159,160].
In recent years, the MD research attention has gone into preparing
customized membranes for MD applications. Some approaches applied
for the current and perspective trends in membrane fabrication for MD
applications have been comprehensively reviewed [158]. The ultimate
performance of MD is largely associated to the membrane properties.
In general, membranes used in MD process should have low resistance
against mass transfer and low thermal conductivity to avoid heat losses.
Typically, porous hydrophobic membrane that is not wetted by the liq-
uid transport but only allow the transportation of vapour is of particular
interests. Membrane materials, membrane thickness and porosity are
some of the parameters that need to be carefully optimized to ensure
excellent features for MD applications. The phenomenon of flux deteri-
oration in MD is common in long-term operation and transmembrane
flux decline as a consequence of fouling and temperature polarization
when the system is operated under high convection flux [157]. As MD
involves different transport phenomena, the nature of fouling in MD is
different from other pressure-driven membrane processes [158]. Fur-
thermore, the hydrophobic nature of the membranes has also intensi-
fied the susceptibility of MD towards organic fouling. While most of
the conventional techniques applied for fouling and concentration
polarization reduction in pressure driven membrane processes are in-
appropriate for MD process due to high energy consumption, several
hydraulic techniques have been established to reduce fouling and
thermal polarization in MD. Some interesting and promising techniques
include induction of secondary flow, pulsating and intermittent flows
and air sparging [161]. However, one of the exasperating impacts is
the additional operational and capital cost associated with the equip-
ment used.
3.4. Membrane capacitive deionization
CDI is a long existing desalination technology which has never been
made in industrial deployment due to deficiencies in cost and salinity
limits, despite its less energy intensive compared to RO and thermal de-
salination. In brief, the salt solution is allowed to flow through the MCD
module which consists of numerous pairs of high-surface-area elec-
trodes with high specific surface area (400–1100 m2/g) and a very low
electrical resistivity (less than 40 mΩ cm) [99]. The polarization of
each electrode pair is then initiating the electrosorption of anions and
cations in solution and later on, the saturated electrodes are regenerated
by desorption of the adsorbed ions under zero electrical potential or re-
verse electric field. On the other hand, as the name implies, MCDI is a
modified system obtained by inserting two ion exchange membranes
53
into the conventionally used CDI to tackle the shortages of CDI in several
ways [99,162]. In principle, MCDI relies on the applications of an
electrical potential difference between the two oppositely placed po-
rous electrodes where in front of which ion-exchange membranes are
placed. Operating MCDI at constant current mode can produce freshwa-
ter with a stable effluent concentration. While the conventional CDI suf-
fers a major problem during the regeneration step where the residual
ions left from the incomplete regeneration accumulated and blocked
the way of other ions during the next purification step, the ion exchange
membranes introduced in MCDI system can assist in preventing
adsorption during the regeneration process [163]. Furthermore, these
ion exchange membranes also capable to keep the co-ions in the inter-
particle pores of the electrodes which in turn enhance the salt adsorp-
tion efficiency. Most impressively, the required energy input of MCDI
is lower than that of CDI as well as very energy efficient compared to
its RO and MD counterparts, particularly for salt removal from streams
where the ion concentration is already relatively low [164].
Like other desalination technologies, the performance of MCDI
greatly depends on the optimisation of the material and process. A
proper selection and optimization of ion-exchange membranes with
high ion selectivity and good chemical durability is crucial to further en-
hance the ion exchange capacity and electrical conductivity to render
low resistance [165]. Additionally, research have also been dedicated
to the development of electrode materials with improved charge and
discharge kinetics. The electric capacity electrodes must be increased
and the proper sorption mechanism should be selected in order to in-
crease the storage of ions in the electrodes and to improve the rate
and efficiency of salt removal. Recently, MCDI device using CNT elec-
trodes is of favours to minimize ion desorption during electrosorption.
With the right combinations of enhanced materials and optimized sys-
tem operation, the salt removal capacity of MCDI was found to be 50%
higher than that of CDI system [166].
3.5. Integrated membrane system
There has been growing emphasis on membrane-based seawater
desalination technology, particularly integrated membrane system
(IMS) that combines multiple classes of desalination systems with
different beneficial characteristics [167]. The IMS is a breakthrough
solution that is win-win as it can achieve consistently more than the in-
dividual system could. The interconnections of the systems that com-
plement each other can provide a route to minimize the limitations
and barriers that restrict their widespread applications. In a broad con-
text, IMS is a promising way of improving the overall membrane oper-
ation by lowering membrane fouling rates, energy consumption, and
operating cost, hence resulting in a more stable and reliable desalination
operation. Table 2 summarizes some of the advantages of the IMS.
A hybrid system which consists of FO followed by conventional RO
has recently been investigated [108,138,168]. In this system, FO can be
effectively utilized as an RO pre-treatment process, where the retained
brine from RO is re-circulated to the FO modules and then used as a
draw solution [98,169]. When the FO unit is installed prior to the RO de-
salination plant, the seawater is used as the draw solution and is diluted
before entering the RO system. Low hydraulic pressure can be applied to
the subsequent RO as a driving force to produce fresh water from the di-
luted seawater, hence significantly lowering the energy required for the
RO desalination. Furthermore, the fouling potential in the RO mem-
brane can be also dramatically lowered with the presence of FO as the
pretreatment unit. As no or only low hydraulic pressure is applied, FO
exhibits good fouling reversibility for which a pilot study has demon-
strated that FO membrane fouling in a pilot-scale FO–RO hybrid system
was largely reversible after 1300 h operation [138,170].Through the im-
plementation of FO in the commercial pressure driven RO system, the
desalination plant could exhibit low fouling tendency, improved recov-
ery factor and reduction in the use of chemicals at the pre-treatment
stage [98,171]. Since the feed solutions for the FO process can be diverse
54 P.S. Goh et al. / Desalination 391 (2016) 43–60
Table 2
The features of various hybrid modes for desalination.
Hybrid mode Features/advantage
FO–RO • FO as the pretreatment of RO
• Lower applied pressure for subsequent RO
• Lower RO fouling
FO–PRO • Reduce the concentration of saline waste
• Power generation
FO–MD • Draw solution generation
• Increase FO flux
• Allow robust feed condition
PRO–RO • PRO as the pretreatment of RO
• Reduce the concentration of saline waste
and high quality product water can be obtained, FO–RO hybrids system
can be promisingly used along coastal locations.
A dual-stage FO–PRO process for hypersaline solution treatment and
power generation has also been proposed [172].The treatment process
can significantly reduce the concentration of saline wastewater to
allow direct disposal to sea. The hybrid system can not only reduce
the TDS of the hypersaline solution but also generate a useful power
from the osmotic pressure gradient across the FO membrane through
the PRO unit. To expand and fully harvest the advantages of MD process,
new MD applications and hybrid systems have be explored. Incorpora-
tion of MD into the desalination process can dramatically reduce brine
discharge and therefore enhance water recovery. When coupled with
other desalination processes such as RO, MD can increase the recovery
factor and enhance the overall process efficiency by treating the RO
brine [173,174]. Meanwhile, as mentioned earlier, a sustainable FO sys-
tem must be equipped with second separation process to generate draw
solute and produce clean water. An integrated FO–MD system as shown
in Fig. 5 has been attempted to achieve this purpose [175].As a process
driven by extensive thermal energy, the FO–MD process is of great in-
terest when solar energy or waste heat is abundantly available. Since
MD is usually operated at high temperatures with the aid of waste
heat or solar panels, the draw solution can be recycled at higher temper-
ature compared to stand-alone FO unit, hence increases the FO flux.
Owing to the low susceptibility of FO process towards fouling, the hy-
brid FO–MD process can be sustainable under robust feed conditions
[151]. In a typical FO–MD process, the FO process serves to draw clean
water from the feed solution to the draw solution side, meanwhile the
MD process is utilized to reconcentrate the diluted draw solution
[176].The FO–MD desalination process investigated by Wang et al.
using hydroacid as draw solution demonstrated the highest seawater
desalination flux of 6 LMH and 32 LMH for FO and MD, respectively
[175].
Fig. 5. An integrated FO–MD system which allows the FO process serves to draw clean water from the feed solution to the draw solution side, meanwhile the MD process is utilized to
reconcentrate the diluted draw solution [175].
PRO can effectively function as a supplementary technology to im-
prove the performance and sustainability of conventional desalination
processes. PRO hybridization with desalination technologies, especially
FO and RO, was found to be very promising to simultaneously ease
water scarcity and energy stresses. Currently, there is an increasing
trend of coupling PRO process with RO process to reduce the cost of de-
salination while enhancing the power generation in PRO [130,177–179].
This target can be achieved through either diluting the seawater with
PRO permeates or utilise the concentrated brine of RO as a draw solution
of PRO [75]. Furthermore, the PRO dilutes the concentration of the brine
and eventually reduces environmental impact of brine discharge to sea.
As such, the integrated system has the potential to reduce the cost of sea-
water desalination as well as the cost of post-treatment for brine disposal
[180]. Although the hybrid system requires more membrane area, over-
all the system can still be beneficial to reduce the total desalinated water
cost as the energy cost is much more than the membrane cost [181].
However, it should be noted that the advantages of PRO–RO hybrid sys-
tem for practical application can only be realized if an optimized low cost
fouling control strategy such as anti-scaling pretreatment is employed
and high fouling resistant PRO membrane is developed [182]. RO–PRO
hybrid configurations can be varied in terms of the sequence of each sys-
tem and the influent concentration [179]. In brief, when the RO process is
located prior to the PRO, the direct use of low-saline water as a feed so-
lution of PRO is less advantageous for the power production of PRO since
the concentrated brine of the RO significantly reduces the driving force
for the power generation of PRO. However, the effective brine manage-
ment can be achieved when the concentrated brine of the RO is used
for a draw solution of the PRO plant where PRO process is configured
to dilute the brine concentration. Furthermore, the concentrated brine
of RO can improve the ability of a draw solution to draw water from
the feed channel, which is beneficial for the PRO power generation. On
the other hand, when the RO process goes after PRO process, the PRO
process can act as a pre-treatment of the RO process.
4. Challenges and future outlook
With water shortage issue that is lingering around the world, commu-
nities are turning to desalination as the ultimate strategy for reliable
water supply. Membrane technologies are playing a growing role in
meeting water supply and water treatment needs for municipalities
and industry. The various techniques both as stand-alone units and in
integration can address the different water qualities. Moreover, the pos-
sibility of operating plants with different capacity together with central-
ized and decentralized systems according to the specific requirements
in the given area makes membrane technologies an interesting answer
for water issues [98]. As the cost and energy consumption for desalination
 P.S. Goh et al. / Desalination 391 (2016) 43–60
are important factors to minimise the environmental impact of desalinat-
ed fresh water supply especially in remote areas where little options are
available, the extent to which the role of membrane technology further
expands depends largely on their cost-effectiveness. Other than the desa-
lination performance and efficiency, the energy use, concentrate disposal
options and environmental and health concerns are among the top issues
dictating the technology's adoption.
The focus of the membrane research community is geared toward
designing and creating a reliable membrane that is very suitable for de-
salination in which it can continue to function in all commercial envi-
ronments to handle the hiking expectations of the desalination
industries. While nanotechnology is turning into a mature technology,
the emerging nanomaterials are directly participating in the water
treatment field by providing rapid and effective removal of contami-
nants. The convergence between nanochemistry and membrane sci-
ence will likely yield a new generation of active membranes endowed
with different attractive functionalities. A membrane that possesses all
desired properties to achieve complete rejection and improve the flux
in multiple folds would represent an attractive proposition to industry.
However, one of the biggest constraints to transform the advanced
functionalities of these novel membranes into industrial realization is
associated to their scaling-up into designed products that can be eco-
nomically mass produced [183]. The investors should recognize that it
is not a one-off exercise to develop an economically viable manufactur-
ing platform that is capable of delivering a product with consistent qual-
ity to the marketplace.
The findings and achievement at fundamental level provide the basic
framework to discover the true innovative potential of the materials. Sev-
eral challenges still need to be addressed to optimize the design of the ad-
vanced membranes for practical applications. Despite their astonishing
properties in ideal conditions, most of the nano-enabled membranes suf-
fer greatly from some inherent limitations such as poor solubility and
processability, which hinders their commercialization for industrial ap-
plications [87]. Hence, extra efforts should be endeavoured to resolve
the issues. Also, the fundamental understandings must first be developed
to systematically evaluate the effects of nanomaterials on the membrane
properties such as surface hydrophilicity, pore size, charge density and
membrane porosity so that they can correspond effectively to the mem-
brane performance changes [4]. For example, since the selectivity across
the active layer of TFN membranes is directly related to the availability
of free volumes [65], the interactions between the incorporated
nanomaterial and the polymer matrix must be well comprehended in
order to design a desalination membrane that can enhance the liquid per-
meation while retaining the salt diffusion across the membranes.
Although the membrane surface properties can be improved by
modifications, either through direct incorporation of the materials with-
in the polymer matrix such as nanocomposite membranes or through
the attachment of materials with surface functionalities on the
membrane surface, several underlying issues should still be taken into
consideration. The first issue is related to the direct contact of the mod-
ified membranes with contaminants during the separation process,
since membrane fouling can only be minimized but cannot be
completely avoided. The next issue is linked to the potential release of
nanomaterials from the nanocomposite membrane, which would raise
health and safety concerns [7]. In this concern, it is of high priority to en-
sure that nanotechnology is incorporated into desalination technology
in a safe, responsible and sustainable manner. As such, an informed as-
sessment of the potential human health and environmental impacts
upon the contact of nanomaterials with water body must be carefully
conducted. In spite of their capability to offer several advantages, anoth-
er obvious issue is the high production cost associated to complicity of
nanomaterial synthesis, which has also prompted the search for more
economical yet effective option [28]. It is also worth noting that the de-
velopment of novel membranes is mainly based on the studies per-
formed from the perspective of materials science, with focuses placed
on the physicochemical and morphological characteristics of the
55
newly designed and synthesized materials. Prior to their commerciali-
zation, still insufficient attention has been devoted to the complexity
and interactions of the membrane materials in water body. Additionally,
through the progresses made in molecular simulation, the outstanding
features of graphene for the development of novel desalination mem-
branes have been well acknowledged. The unique properties such as
high tensile strength as well as controlled pore and porosity open the
doors to construct extremely thin membrane with size tunable pores
to facilitate high water passage rate. Besides that the ability to manipu-
late and fully exploit the properties of some of the discussed
nanomaterials, such as aquaporin and graphene nanosheets remain lim-
ited hence further innovations and revolutionary approaches are highly
required to develop efficient synthesis and up-scaling method as well as
to enhance reproducibility. The positive impacts of these nanomaterials
in water treatment are likely to be based on the ability to conceive of
and build devices that actively function at the scale of the material itself.
Such devices might combine functions such as energy harvesting and
treatment, detection or control [184].
Presently, the assessment on the relationships among the properties
of nanomaterials, the characteristics of the resultant nanocomposite
membranes and the membrane system and operations are still inade-
quate to provide further insights on the practicability of the materials
for commercial desalination processes. Currently, only nanocomposite
membranes have been commercialized while others are still under fun-
damental developmental stages [99].When the cost of energy and
membrane is considered, the benefit of developing high performance
membranes with higher permeability and fouling resistance is insuffi-
cient to be main driver for lowering seawater desalination costs. Thus,
other factors such as process improvements which include lesser pre-
treatment and effective brine management need to be considered to
lower the overall desalination costs [99].
With increasing number of plants built in water-stressed countries
to complement existing water resources, RO is unquestionably the
most ubiquitous technology for desalination. The emergence of these
new and advanced technologies which are still in the laboratory phase
implies that despite the maturity and reliability of the existing commer-
cial processes for desalination, the advancement in material sciences
and engineering still strive to diversify the options for desalination. Cur-
rently, ODMPs, MD and MCDI may not be the main stream in their
realms, but they are increasingly becoming a topic of some interest
and the attention devoted to the related research apparently hikes at a
steady pace. Through the advancement made in all aspects, the emerg-
ing desalination technologies offer unprecedented desalination perfor-
mance that outperforms the conventional technologies. Owing to their
interesting features, it is clear that ODMPs can pose an impressive
array of potential benefits not only in the laboratories, but also when
they are up-scaled and deployed in the real field. The low hydraulic
pressure needed during the process is beneficial to render low energy
consumption, which eventually ensures process costs cut down. While
the security of global energy supplies continues to be problematic, the
striking points of FO seem in place to offer alternative solutions. Mean-
while, a properly designed MD process features unique benefit to treat
highly saline brines that cannot be treated by conventional desalination
processes and makes it an ideal candidate to desalinate concentrated
brines from thermal desalination plants to augment fresh water produc-
tion from existing facilities. Albeit the growing numbers of studies are
conducted, the applications are still explored at a laboratory scale. For
instance, the current research of FO is mainly directed to enhance the in-
trinsic transport properties of membranes on a molecular level
[161].The implications of these improvements on the energy efficiency
of different FO desalination processes remain unexplored. Further de-
tailed investigations and conceptual proofs are highly needed to pro-
mote FO as a mainstream treatment process [6]. Additionally, despite
the similar osmotic concept that lies behind RO, FO and PRO, develop-
ment of versatile membrane materials and structure is still a great chal-
lenge. Although the osmotic power technology has been growing
56 P.S. Goh et al. / Desalination 391 (2016) 43–60
rapidly, the generation and utilization of osmotic power still remain
several years away from commercial viability. For example, although
the potential of PRO technology has prospered. Recent studies have
also pointed out that the power density should be at least higher than
5 W/m2 to make the system economically feasible [114]. The goal to at-
tain high performance membrane with high water permeability and salt
selectivity, which are coupled with customized support layer that sup-
presses the detrimental effect of ICP, can be reached with the break-
through in the material sciences and engineering to make a big leap
for the production of membranes that will be useful for commercial os-
motic power production.
In terms of IMS, the positive and encouraging findings open up the
prospective of employing hybrid systems that integrate FO, PRO, MD
and conventional pressure driven processes for seawater/brackish desali-
nation. Nevertheless, as the development of RO–PRO or FO–RO hybrid
processes is still in their infancy stage, more research and real field data
are important to ensure the viability of this hybrid system before it
marches into the industry large scale operation. Above all, in order to fore-
see the economic niche of these emerging technologies, a reliable cost
analysis is crucial to assess the efficiency of the various hybrid system con-
figurations by considering all key parameters and factors such as energy
production/consumption, water production, capital construction costs,
labor costs, and maintenance costs. A holistic analysis that covers not
only the thermodynamic comparison, but also details such as pressure
fluctuation and pretreatment and solution recovery can reflect the practi-
cal but not the idealised conditions of the system, hence can provide fur-
ther understanding on how they will fit within the desalination industry.
Despite the impressive potential and effectives of these emerging
membrane desalination processes, membrane fouling still exists as the
most detrimental hiccup of membrane-based desalination technologies.
In view of the adverse consequences of membrane fouling to the overall
performance and practicability of the processes, the fouling mechanisms
and the control strategies must be carefully studied to mitigate the persis-
tent issue. Similar to their RO counterpart, these membrane processes are
inevitably susceptible to macromolecules organic fouling, inorganic scal-
ing and biofouling. However, due to the unique features with respect to
their working principle and applied hydraulic pressure among these de-
salination processes, the membrane fouling behaves differently in some
cases. Therefore, in depth research and evaluation must be performed
in accordance to their working principle and operating conditions.
From an industrial perspective, the challenges of a sustainable water
future present a high potential for growth, as well as business opportuni-
ties in sectors related to water. Although it may not be immediately ap-
parent that these new membrane and membrane systems are beneficial
to invest in, the deterioration of competency and reliability of the
existing desalination technologies seemingly far outweighs the cost of
investment. However, the adoption of new technologies strongly de-
pends on the cost effectiveness. Therefore, it is important to implement
the technologies with minimal changes to the existing infrastructure.
In this context, retrofitting and upgrading of the current desalination
plants seems to be a more promising approach. Incorporating innovative
and sustainable materials and processes into currently existing facilities
can seemingly treat the challenging water needs at only a fraction of
the cost of expanding or building more expensive water treatment
plants. The feasibility and versatility of emerging technologies have
brought about huge leap forward both in the industrial world and in so-
ciety. Leading edge membrane technology has advanced to such an ex-
tent that the emerging separation systems can operate extremely
reliably through more efficient and cost-effective techniques to produce
fresh water of high quality.
5. Concluding remarks
Recognizing the plethora of alarming crisis associated with water
scarcity, industry and academia are now seeking for more options to
enhance water treatment efficiency. Undoubtedly, desalination
technologies based on membrane and membrane system are the an-
swers to this global issue. In fact, we have seen an increase in technology
breakthroughs and investments in the past 10 years where the advance-
ments made in membrane and membrane system are aimed at alleviat-
ing stressed water supplies, as well as minimizing overall consumption,
energy use and costs associated with producing and recycling water.
The interdisciplinary research offers leapfrogging opportunities to
develop next-generation membranes for water supply system. As
highlighted in this review, the intrinsic properties of desalination mem-
branes can be drastically altered through the incorporation of
nanomaterials or membrane surface modifications where some of the
drawbacks of current desalination techniques could be avoided by
inventing more efficient and customized membrane materials. The in-
troduction of nanomaterials during the membrane formation has been
the subject of interest as the presence of the carefully selected
nanomaterials with desired properties could render favourable changes
in the membrane morphology and performance. The growing impact of
advanced membranes in desalination has arisen from the new function-
alities offered by the additive materials or surface functional groups
which serve as the tools for providing the desired features. Surface mod-
ifications of polymeric membranes allow the tailored alteration of sur-
face properties in terms of hydrophilicity, roughness and porosity,
hence allow emergence of a new class of novel membranes to potential-
ly combat some underlying issues of the commercial membranes. Fabri-
cation of the desalination membrane with specific functional properties
is scientifically promising and commercially profitable. However, one
should bear in mind that, nanotechnology-based solutions in the
water sector will find wide applications only when they are low cost,
highly efficient, and able to provide clean drinking water in very remote
regions. It is expected that substantial initial investment would be need-
ed to incorporate or switch to nano-enhanced desalination. However,
once adopted, these techniques could considerably lower water treat-
ment costs over the long term. In this article, several advanced technol-
ogies for desalination namely FO, PRO and MD are reviewed. Some of
these stand-alone or hybrid technologies have been commercialized
or are close to commercialization but some are still at their early explo-
ration stage. Inevitably, all emerging membrane desalination processes
might be plagued by the potential challenges associated with limited
experience on scale-up, process design and mode of operations as well
as some pretreatment issues on seawater/brine sources. In order to ad-
vance the technical knowledge in these technologies, field studies must
be deployed to evaluate their feasibility at a pilot scale.
When we put aside the overwhelming momentum and expecta-
tions, on a longer time scale, key questions still remain as to the
technology's long-term durability and performance in a full-scale oper-
ation. Would these novel membranes survive from the harsh conditions
in the commercial environment? Could these emerging desalination
technologies provide holistic solutions to the limitations of the existing
pressure driven membrane processes? It is obvious that, clear protocols
and assessment indexes that serve as the guideline for the selection of
the most promising materials and operating conditions, accurate
modelling for an easy scale-up and full mode operation as well as signif-
icant multidisciplinary research efforts are desired to contribute to the
progresses of the technologies. To conclude, not all breakthroughs
made in the field of desalination science and engineering can be certain-
ly transformed into realities to break the existing boundaries. While
some advances have been made to move from laboratory to industry
in order to close the gaps between fundamental research and practical
applications, it is anticipated that those which currently strive at the
stage for innovations will surely emerge in the not-too-distant future.
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