Desalination 434 (2018) 60–80

Contents lists available at ScienceDirect

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

A review on inorganic membranes for desalination and wastewater T

treatment
P.S. Goh⁎, A.F. Ismail⁎
Advanced Membrane Technology Research Centre, Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, Johor, Malaysia

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

Keywords: The sustainability of global clean and safe water supply is one of the grand challenges facing the world.
Inorganic membranes Membrane technology based on polymeric membranes is one of the most important and widely recognized
Desalination technologies for desalination and wastewater treatment. While polymeric membranes are known to be plagued
Wastewater treatment with some bottlenecks, the technical progress and the accompanying knowledge in inorganic membrane de-
velopment have grown inexorably to solve some of the underlying issues. Aside from the conventionally used
ceramic membranes which based on metal oxides, nanostructures such as zeolites, metal organic frameworks
and carbon based materials have sparked enormous interest in the preparation of inorganic membranes owing to
their tunable nanoscaled structural properties that can render excellent rejection and/or ultrafast water trans-
port. This review provides insights into the physico-chemical properties and fabrication approaches of different
classes of inorganic membranes. The transport mechanisms that are associated to their unique structural features
are also discussed. Furthermore, the performance evaluation of these inorganic membranes in a wide spectrum
of desalination and wastewater treatment applications are also elaborated. Finally, the challenges in the de-
velopment of inorganic membrane for practical commercial application are identified and the future perspec-
tives are presented.

1. Introduction
Industrialization and urbanization are the linchpin to the global
economic growth and development that has significantly contributed to
the human welfare. Unfortunately, they have also led to increasingly
uncontrollable discharge of wastewater and consequently created a
series of environmental problems that associate to the climate changes.
As water usage is a key operational part in most of the industrial pro-
cesses, the production of wastewater is inevitable in a wide spectrum of
industries [1]. With more preeminent economic growth, wastewater
discharges from both industrial and municipal sources have also grown
at the similar pace. Water pollution has led to the build-up of en-
vironmental contaminants where increasing evidences of pollution and
deterioration of water quality have been witnessed in more developing
countries. In order to restore the environment and deter the hazards to
mankind, various approaches have been targeted to treat the industrial
waste [2–5].
In another worsening scenario, continuing population growth, ur-
banization and industrialization have also resulted in alarming global
water demand. In fact, with the water consumption that has been es-
calating at more than twice the rate of the population in the last
century, water scarcity is among the most chronic issues that challenges
the mankind and world in the 21st century. The United Nations predicts
that in the coming decade, half of the countries worldwide will confront
with water stress if not outright shortages. Desalination and water reuse
has been long acknowledged as a feasible mainstay to address this
grand challenge by offering safe and clean water in many arid areas,
coastal regions or remote locations. Particularly for water-scarce
countries such as Middle Eastern and North Africa Countries that have
attempted and implemented all other measures to secure fresh water,
desalination may serve as the most viable approach to supply fresh
water supply hence to allow sustainable development and support po-
pulation growth in this modern society [6]. Membrane and other na-
noporous materials have been considered as the essential technologies
to address global water shortage problem [7]. Extensive product line of
water and wastewater filtration systems such as conventional pressure
driven seawater and brackish water reverse osmosis (RO), nanofiltra-
tion (NF), ultrafiltration (UF) and microfiltration (MF) as well as os-
motically driven forward osmosis (FO) and pressure retarded osmosis
(PRO) have been introduced in the market [8–13]. Emerging desali-
nation technologies such as microbial fuel cell and membrane capaci-
tive deionization also found increasing importance in combating water

⁎
Corresponding authors.
E-mail addresses: peisean@petroleum.utm.my (P.S. Goh), afauzi@utm.my (A.F. Ismail).

http://dx.doi.org/10.1016/j.desal.2017.07.023
Received 30 April 2017; Received in revised form 18 July 2017; Accepted 31 July 2017
Available online 12 August 2017
0011-9164/ © 2017 Elsevier B.V. All rights reserved.
P.S. Goh, A.F. Ismail
issues [14,15]. At the academic level, fundamental, applied and trans-
lational research related to desalination technologies are actively
blooming as the result of the material sciences and engineering ad-
vancement made in this field [16,17].
Undoubtedly, polymeric membranes are currently in the forefront of
desalination and wastewater treatment membranes due to their well
establishment and excellent long term track records. Today, the in-
dustry market based on polymeric membranes for water purification is
impressively huge. Contemporary researches have been conducted to
address several challenges related to material-based limitations posed
by polymeric membranes to resolve the issues with the best practice
solutions. One of the critical issues in the use of polymeric membranes
in desalination and wastewater treatment deals with the trade-off re-
lationship between permeability and selectivity as well as membrane
fouling and scaling. The adverse effects towards sustainable application
of polymeric membranes for water purification have triggered great
interest in improving the properties of polymeric membranes through
different strategies of modification. One of the most impressive and
state-of-the-art achievements in this field is the development of mixed
matrix membranes (MMMs) and thin film nanocomposites (TFNs) [18].
The innovation that combines the unique features of both polymeric
matrix and inorganic fillers has emerged as a promising solution for the
underlying problems.
While development of polymeric membrane is progressing in a
steady pace, inorganic membranes with exceptional chemical and
physical properties, high tunability and reusability have also gained a
growing interest. In a broad term, inorganic membranes consist of
ceramic membranes and carbon-based membranes. Oxides such as
alumina, silica, titania or the mixtures of these components are some of
the commonly used commercialized ceramic membranes [19]. From
maintenance and economical point of view, inorganic membranes are
ideal for in-place chemical cleaning where high temperatures and
subsequent chemical cleaning can easily bring about sustainable flux
recovery. More importantly, inorganic membranes are less susceptible
to the deterioration by bacteria, which are responsible for the bio-
fouling degradation of most polymeric membranes [20]. Depending on
the materials' nature, inorganic membranes can be fabricated in thin
film and multi-layer supporting structures with adequately strong and
permeable characteristics or they can also be made in self-supporting
structures as standalone sheets and tubes if they are sufficiently
permeable [21]. A typical ceramic membrane is made up of a macro-
porous support layer and a meso- or micro-porous active layer. His-
torically, due to the unfavourably high manufacturing cost and diffi-
culties in handling, the industrial use of inorganic membranes in water
reclamation was uncommon [22]. In fact, at commercial scale, in-
organic membranes have only been more acceptably used in the ap-
plications that represent great challenges to the conventionally used
polymeric membranes such as extremely high temperature as well as
harsh and highly contaminated feed environment. Recently, the pre-
paration of low cost ceramic membranes with composition mainly
based on affordable clays and organic pore formers, with the cost more
similar to that of polymeric membranes, has encouraged the prevalence
of ceramic membranes at larger scale [23–26].
Desalination and wastewater treatment using inorganic membranes
is an attractive alternative for some challenging water treatment pro-
cesses such as wastewater containing radioactive substances and highly
concentrated organic effluents, oil and grease where the conventional
polymeric membranes are either inapplicable or inefficient due to se-
vere fouling and material instability issues [27–30]. Inorganic mem-
branes are also advantageous in brackish water treatment, seawater
pretreatment and high temperature desalination, where high rejection
above 99% is not a critical requirement [31]. These types of industrial
wastewater are normally discharged in large quantity and pose a great
treat to the conventional wastewater treatment system due to their
complex nature and chemical composition [30]. Various computational
and experimental studies have been performed to study the ability of
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Desalination 434 (2018) 60–80
nanoporous inorganic membranes to remove pollutant ions and/or
molecules with different natures and characteristics. The emergence of
some new materials particularly metal organic framework (MOF) and
carbon-based nanostructures such as carbon nanotubes (CNTs), gra-
phene and its derivatives has offered a new era for enabling membrane
science and technology with accomplished separation performance. The
unique features of these materials have been promptly harnessed to
design a radically new kind of inorganic membrane. Free standing in-
organic membranes fabricated from nanomaterials such as CNT, gra-
phene and MOF have been touted as the next big thing in membrane
technology. The high permeability and selectivity of these membranes
could allow higher water flux and show improved energy savings at
high recovery. As such, these materials offer huge opportunities for the
implementation of commercial plants with smaller footprint. Besides,
the new structural concepts of these membrane materials are antici-
pated to ameliorate some existing issues found in the contemporarily
used materials and accomplish the practically efficient, high pro-
ductivity and energy saving desalination and wastewater treatment
processes.
In the interest of the growing potential of inorganic membrane in
desalination and wastewater treatment, this review compiles the con-
temporary advancement and remarkable achievements made in this
field. The first part of this review focuses on the structural properties as
well as the common design, fabrication and modification approaches
for various inorganic membranes. The theoretical and empirical
knowledge in the fluid transport phenomena and mechanisms of in-
organic membranes is also covered to provide understanding on the flux
and rejection behavior of the membranes. In the second part of this
article, the performance evaluations of various inorganic membranes in
desalination and several important wastewater treatments are high-
lighted. The potentials of ceramic membranes and carbon-based in-
organic membranes in treating oily wastewater, dye and organic com-
pounds, inorganic ions, heavy metal and radioactive ions are
comprehensively elaborated based on the recent and current publica-
tions. Finally, the challenges, issues as well as the opportunities of in-
organic membranes in advancing membrane technology are also ad-
dressed.
2. Inorganic membranes
2.1. Ceramic membranes
Ceramic membranes could be made from typical metal oxides
(alumina, silica and zirconia) aluminasilicate zeolite as well as recently
emerging metal organic framework. In this section, several classes of
ceramic membranes made from different inorganic materials are dis-
cussed.
2.1.1. Metal oxide membranes
Ceramic membranes with a wide range of insoluble oxides have
shown interesting separation and processing properties. Out of these,
mesoporous membranes zirconia and titania have been applied in the
industry. Conventionally, a porous metal oxide based ceramic mem-
brane is characterized by a multi-layered asymmetric structure which
composed of a thicker support layer with relatively large pores
(~ 0.5 μm) to provide mechanical integrity for the membrane systems,
an intermediate layer to reduce pore size to mesoporous dimensions
(2–5 nm) and a much thinner top layer with small and selective pores
(< 1 nm) for selective separation [32,33]. Sol-gel is one of the most
feasible methods for the preparation of metal oxide ceramic mem-
branes. Depending on the media or solvent used, this technique can be
further divided into the colloidal and polymeric sol-gel routes. A two-
step process has been commonly applied to obtain colloidal sols from
oxide precursors, i.e. precipitation of a condensed and hydroxylated
species from hydrolyzed precursors followed by the transformation of
precipitation into a stable sol through a peptization reaction [34].
P.S. Goh, A.F. Ismail Desalination 434 (2018) 60–80

Typically, the fabrication of a porous membrane involves multiple steps

where the coating of intermediate layer and final separation layers are
normally performed on the prepared support layer. High temperature
sintering is normally required to combine these layers. In fact, the
complexity in the membrane fabrication and their expensive starting
materials have concertedly resulted in the high production cost of
ceramic membrane. As such, simplifying the multistep fabrication steps
as well as the use of cheap and natural raw materials have been iden-
tified as the most straightforward approaches to reduce the ceramic
membrane production time and cost.
Mesoporous γ-alumina membrane, one of the most widely in-
vestigated ceramic membranes, usually served as interlayers for
ceramic NF membranes. A typical mesoporous γ-alumina membrane is
characterized with an average pore size of 3–5 nm which corresponds
to a molecular weight cut-off (MWCO) of 3000–10,000 Da [34]. Alu-
mina membrane with average pore size of about 1 nm has also been
attempted. However, due to the tight pore structure, the permeance of
the membranes was normally below 5 L m− 2 h− 1 bar− 1 hence in-
sufficient to meet the industrial expectation. Recently, solvent resistant
1.61 nm alumina NF membrane with high permeability of
17.4 L m− 2 h− 1 bar− 1 has been reported [35]. In distinction to the
conventionally prepared metal oxide based ceramic membranes con-
taining three layers, some recent studies proposed an attractive ap-
proach of serving the mesoporous interlayer as the top layer as a se-
parating medium for pervaporation desalination [33,36–40]. This
innovative strategy reduces the membrane's preparation costs by ex-
cluding the requirement for additional top layers. Additionally, the Fig. 1. Schematic illustration of percolative porous pathway and diffusions of water and
hydrated salt ions through (a) microporous constrictions that only allows the passage of
reduced membrane thickness can also effectively minimize the re-
water molecules and (b) mesoporous region that non-selective to small amount of hy-
sistance of water diffusion through the membrane and increase the drated salt ions [36].
water flux. Selection of cheap starting materials for ceramic membrane
development can deal with a dual economic and environmental benefit.
Coal fly ash, the by-product produced after the combustion of raw coal improvement of their filtration performance. Native metal oxide
in power plants, has been used as raw material to fabricate mullite ceramic membranes possess abundant surface hydroxyl groups (eOH)
(3Al2O3·2SiO2) and cordierite (2MgO·2Al2O3·5SiO2) ceramic membrane hence are normally characterized by hydrophilic surface [47]. The
supports with addition of Al- or Mg-source materials such as dolomite hydroxyl groups on the membrane surface can be harnessed as reactive
to control the porosity, pore size distribution and microstructures sites for the introduction of hydrophobic organic moieties. Compared to
[41–43]. the pristine hydrophilic metal oxide membranes, hydrophobized
In general, most of the porous metal oxide ceramic membranes ceramic membranes hold wider field of applications, particularly in
perform separation based on the increase of size by hydration and membrane distillation and pervaporation [48]. Grafting of ceramic
electrostatic effects at the pore entrance [21]. For the treatment of ty- membranes with surface functional groups such as silane groups has
pical industrial wastewater that consists of the mixture of metallic ions, been frequently applied to modify the metal oxide and/or membrane
organic and inorganic substances, the rejection is primarily governed by surfaces to enhance the hydrophobicity or/and narrowing pore size.
the strong electrostatic interactions developed between the multivalent Fluoroalkylsilanes (FAS) is one of the most adaptable organosilane
cations and the positively charged metal oxide ceramic membranes compounds to be grafted onto the pore wall of the metal oxide and their
[44]. Such rejection mechanism depends strongly on the pH of the feed ceramic substrate [49–52]. Several interesting surface structures and
solution and the modification of the membrane surface charge. Instead functionalities can be formed on the metal oxide ceramic membrane
of possessing uniform meso or microporous structure, some oxide-based surface. With hydrolysable groups on one end and organic moieties on
ceramic membranes such as amorphous silica membrane exhibit a tri- the other, FAS can react with the hydroxyl groups on the metal oxide
modal pore size distribution, consisting of small 3 Å and large 8 and surface to form stable covalent bonds. Under the sequential reactions
12 Å that are responsible for different separation pattern [36]. As de- that involve hydrolysis and condensation, stable Al-O-Si bonds can be
picted in Fig. 1(a), the salt rejection is mainly contributed by a perco- formed between FAS and oxide surfaces. Another plausible binding
lative pathway containing constrictions with size smaller than that of route involves the reaction between the hydrolyzable group of the or-
hydrated salt ions but greater than that of water. On the other hand, the ganosilanes with other organosilanes to form a polymeric layer in the
percolative pathways which composed of mesoporous regions linked to presence of water. It is also suggested that the anchoring efficiency is
microporous constrictions or to another mesoporous region may result dependent on the length of the FAS hydrophobic chains where shorter
in the passage of small amount of salt through the membrane, as illu- chains can be linked with higher efficiency [53].
strated in Fig. 1(b). Study has also shown that the removal capability Another prominent outcome of the surface modification of metal
can be achieved through the combination of filtration and the ad- oxide ceramic membrane is the increasing fouling resistance of the
sorptive properties possessed by the reactive surface functional groups. membranes, especially in the treatment of water-in-oil (W/O) emul-
For instance, the active silanol group on the surface of nanosilica sions [54]. Through the careful selection of surface modifying agent,
membrane could interestingly provide adsorptive active sites to bind the membrane pore diameter and structure remain unmodified to
and remove dye ions from aqueous solution [45]. maintain the separation performance. Studies showed that self-as-
Membrane surfaces play a major part in affecting other properties of sembled monolayer of alkoxysilane such a hexadecyltrimethoxysilane
membranes such as hydrophobicity, surface charges, hydrodynamics (HDTMS) can effectively reduce the water droplet adsorption on the
and fouling rate [46]. As such, the surface characteristics of ceramic membrane surface hence mitigate membrane fouling as well as drasti-
membrane have been investigated for the better understanding and cally increase the oil flux and water rejection based on the enhanced

62
P.S. Goh, A.F. Ismail
surface oleophilicity [55,56]. In the typical W/O emulsions filtration,
the ceramic membrane is preferably designed to exhibit hydrophilic
surface to avoid the attachment of W/O emulsion droplets onto the
membrane surface or entering into the membrane pores, consequently
minimize the fouling phenomena. A wide range of hydrophilic nano-
materials such as TiO2, Fe2O3 and graphene oxide (GO) have been
applied to achieve this purpose [57–59]. Pre-coated Fe2O3 dynamic
membrane (DM) with hydrophilic surface with cross section presented
in Fig. 2(b) has been developed to reduce the fouling of ceramic
membrane [57]. Besides rendering high hydrophilicity to facilitate the
removal of oil foulants from its surface by backwash, the Fe2O3 layer
also reduced the exposure of ceramic membrane to oil droplet. More-
over, the dynamic Fe2O3 surface layer which has interacted with oil
particles could be easily washed out by backwash as depicted in
Fig. 2(c). Hu et al. evidenced that covalent bond was established be-
tween GO and Al2O3 ceramic membrane [59]. Owing to the carboxyl
groups that present on the surface, GO was partially ionized to form GO
anions and hydrogen cations thus react with the hydroxyl groups on the
metal oxide surface during the heat treatment. Subsequently, GO was
enriched onto the porous hydrophilic surface when Al2O3 was im-
mersed into the GO aqueous dispersion. As a result, a concentrated GO
coating was finally formed at the solid/liquid interface. Additionally,
some studies have also shown that the optimized cleaning protocol has
resulted in successive 90–95% permeability recovery of a 0.1 μm zir-
conia and 0.5 μm silicon carbide membrane [60,61].
Some studies have dealt with the coating of a thin polymeric layer
onto commercialized macroporous ceramic modules to improve the
separation performance of the ceramic membrane [62–66]. As the
polymer solution tends to penetrate into ceramic pores, one significant
challenge of using macroporous supports to prepare such composite
membrane is the formation of a dense and defect-free separation layer
on it. Additionally, understanding the formation mechanism of polymer
layers at the adhesion surface is also important to optimize the
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Desalination 434 (2018) 60–80
Fig. 2. Cross section images of (a) pristine and (b) pre-
coated Fe2O3 ceramic membranes, (c) schematic illustration
of membrane fouling mechanism and detachment of Fe2O3
by backflush washing [57].
separation performance as it has been acknowledged that the selectivity
and permeation through polymeric membranes are closely associated to
the composition, preparation method, thickness and operating condi-
tions [67]. The general procedure to prepare the polymer coated
ceramic membranes through dip-coating method involves the pre-
paration of coating solution which contains polymer, solvent and
crosslinker, the coating onto the outer surface of the tubular ceramic
support and finally heat treatment. The ceramic supports are usually
polished prior to the dip coating to reduce the surface roughness and
ensure the good quality of the resultant polymer/ceramic composite
membranes [63]. Tubular α-alumina ceramic membrane has also been
coated using cellulose acetate (CA) to reduce the original ceramic pore
size in order to increase the efficiency of the composite membranes
[62]. The coated polymer layer also plays an important role more in
controlling the pore-type diffusion and sorption of molecules onto the
coated surface to attain better contaminant removal.
2.1.2. Zeolite membranes
Zeolites are porous crystalline aluminosilicates with a well-defined
channel structure of molecular dimensions. They accommodate dif-
ferent mono- and divalent cations (Na+, K+, Ca2 +, Mg2 +) hence can
be readily exchanged in a contact solution. Zeolites have attracted at-
tention as potential membrane materials for both gas and liquid pro-
cesses due to their unique molecular sieving properties that can pre-
cisely separate molecules based on the size exclusion ability rendered
by the controlled dimensions of pore channels. Different classes of
zeolite membranes, such as MFI, LTA and FAU have been fabricated for
membrane-based water purification and desalinations. Zeolite mem-
branes possess some exceptional properties that cannot be met by
conventional polymeric membranes. Some of these properties include
thermal and chemical stability, tunable pore sizes and low fouling
tendency [68].
In the past few decades, significant progress has been made on the
P.S. Goh, A.F. Ismail
synthesis approaches of zeolite membrane which have resulted in dif-
ferent membrane morphologies, compositions and separation char-
acteristics. Zeolite membranes can be prepared via one step or sec-
ondary growth approaches [19]. Secondary growth method, which
separate zeolite nucleation from the crystal growth, is a well-estab-
lished and highly reproducible method to fabricate MFI and FAU
membrane when the crucial parameters such as seed formation, layer
deposition and growth conditions are carefully tailored [69]. Zeolite
nanocrystal, more commonly known as nanozeolite, can be readily used
as nanoseeds for the fabrication of dense zeolite films and membranes
via secondary growth based on the superior colloidal properties of their
suspensions [70,71]. In fact, different seeding techniques such as dip-
coating, cross flow and spin coating have been widely used to synthe-
size zeolite membrane with high quality. The synthetic zeolite mem-
branes have been commonly fabricated in thin-film which are sup-
ported on a porous substrate [72]. However, fragility of the substrate as
well as the poor compatibility between the zeolite thin film and sub-
strate have prompted the defect formation hence hampered their
practical application in commercial desalination. More recently, efforts
have been made to explore the use of natural dense zeolite which is free
from macroporosity or fragile crystal grain boundaries. Dense clin-
optilolite has been identified as one of the promising geomorphic nat-
ural zeolites that exhibits desired mechanical robustness industrial
applications [73]. Microwave-assisted heating based on the above-
mentioned synthesis strategies has also been attempted to synthesize
LTA, MFI, AFI, FAU, SOD, and ETS-4 types of zeolite membrane. Under
the microwave irradiation, this fast synthesis approach is advantageous
to promote high membrane rejection as it speeds up the zeolite mem-
brane formation rate hence retarding the impurity and intracrystalline
defect formation [74]. Compared to the conventional heating method,
the overall membrane thickness can be reduced to facilitate the passage
of species at the interface of zeolite film and substrate. As such, high
water flux can be expected as the passage of molecules across porous
membranes is inversely proportional to the thickness of the rate lim-
iting layer [68].
Zeolite membranes was initially applied for gas separation and
ethanol/water separation through pervaporation [75]. Later on, the
computation simulation that predicted 100% salt rejection through a
perfect single crystal had shed some light on the potential of zeolite
membranes for desalination. The application of zeolite membranes for
desalination through pervaporation has been established and showed
great promise for desalination applications [68,73,76,77]. Despite the
first MFI silicalite-1 zeolite membrane experimental attempt that barely
observed 77% salt rejection and a water flux as low as 0.003 m3/m2·day
at 21 bar [78], subsequent innovations have been brought out to
modify the zeolite structure. As zeolite membrane can be a more robust
desalination option based on its chemical resilience, it can be poten-
tially used to avoid the costly pretreatment required by conventional
polymeric RO membranes [79]. Generally, hydrophilic zeolite mem-
branes can be obtained by lowering the Si/Al ratio. However, due to the
stronger stability of SieO bond over that of AleO bond, the chemical
and thermal stability of the zeolite membranes might be compromised
at high Si/Al ratio [80]. To ensure practical application, the poly-
crystalline structure and Si/Al ratio are optimized to enhance the
wettability and membrane surface charge, hence the flux and salt re-
jection. For some Al-rich zeolite membranes, functionalization of the
zeolite cage is also a viable strategy to enhance the membrane se-
paration efficiency. Although most of the past experimental studies
have supported that hydrophilic membranes improved the water flux in
comparison to that of hydrophobic membranes, contradict findings also
stated that, the hydrophobic property of the zeolite subnanometer pore
structure plays a substantial role in offering a desired internal surface
chemistry and facilitating the greater mass flow across the zeolite
membranes [81]. Compared to the one introduced with hydrophilic
defects, the intrinsic hydrophobic pore structure of MFI zeolites
weakens the attraction between the water and the defect-free surface,
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Desalination 434 (2018) 60–80
hence promoting fast water transport.
Up to present, there are still several uncertainties and concerns re-
garding the mechanism of transport and ion rejection through the vi-
cinity of zeolite frameworks. It has been generally agreed that the se-
paration mechanism of zeolite membrane is based on size exclusion and
ions interactions to reject the hydrated ions. As such, the separation
efficiency normally increases with the valency of ions. Theoretically, in
order to reject Na+ and Cl− with hydrated size of 0.72 nm and 0.66 nm
respectively, the intercrystalline interconnection and pore size must be
well controlled below 0.66 nm to ensure high ion rejection. One of the
most studied zeolite class is MFI-type zeolite which has orthorhombic
crystal symmetry with nearly cylindrical, 10-member ring channels
with aperture size of 0.54–0.56 nm and intracrystalline pores of
1.1–1.2 nm [75,81–83]. MFI membranes in flat, tubular mono and
multi channels with various sizes have been developed for pervapora-
tion and RO desalination. Ion rejections up to 99% and 95% were
achieved for pervaporation and RO, respectively [83]. Besides produ-
cing high quality water suitable for reuse, MFI-type membranes are also
bestowed with high tolerance to long term strong chlorine cleaning
[79]. Hydrophilic zeolites such as LTA membranes have also shown
promising ions rejection, but they demonstrated relatively low water
flux for seawater desalination, mainly due to their small pore opening
which was about 0.4 nm [77]. Ideally, defect free zeolites are desired so
that diffusion can only take place through the intracrystalline pores
within the zeolite cage in order to obtain excellent separation perfor-
mance. Unfortunately, preparation of intact zeolite thin film with no
intercrystal pores and other microdefects is always hindered by the
flaws of synthesis such as the insufficient intergrowth of crystals [79].
Moreover, zeolite membrane is a polycrystalline film that accom-
modates nano-sized intercrystal pores. As such, during the passage
through the pores and boundaries, the interactions between zeolite and
the ions in the feed solution could result in the entrance of some ions
into the zeolitic pores and adsorb to the pore surface. This could in turn
modify the diffusion patterns of the molecules and reduce the perme-
ability. Additionally, upon the ion attachment on the external surface
and microporous intercrystal boundaries, overlapping double layers
tend to build up and subsequently hamper ion transport [78]. In most of
the cases, the ion rejection and water flux are the functions of the size
and charge density of the solute ion, as well as of the double layer
thickness which is influenced by the ionic strength and temperature of
the aqueous solution [84]. Recent study indicated that FAU zeolites
with greater hydrophilicity can overcome the water flux and ion se-
lectivity tradeoff by providing enhanced water molecule adsorption and
diffusion through their relatively large pore size [77].
2.1.3. Metal organic framework membrane
MOFs are a relatively young class of functional porous material
which composed of coordination association between metal-containing
clusters and multitopic organic linkers. This unique combination has
rendered the versatility for customizable architectures and chemical
functionalities [85]. Structurally, all MOFs comprise of secondary
building units (SBUs) which consists of metal ions and oxygen atoms.
Hence, the organic linkers act as the bridging agent to connect these
SBUs to form the MOF assembly. A wide spectrum of organic linkers
with different functionalities, ranging from bidentate to polydentate
aromatic carboxylates, have been used to synthesize various eccentric
traits of MOFs [86]. A prudent selection of organic linkers and metal
oxides allow pore sizes, volumes and functionalities to be rationally
controlled at the molecular level, hence resulted in the structural fra-
meworks of different dimensions and topology. The shape selective
MOF nanocrystals with tunable micro- and meso-scale porosity can also
be synthesized by tailoring the crystallization behavior through the
integration of controlled nucleation and growth as well as the 3D self-
assembly processes [87]. MOFs are endowed with large surface area of
6000 m2/g and 90% porosity [88]. Owing to their crystalline structures,
MOFs are mechanically robust and durable to maintain the integrity
P.S. Goh, A.F. Ismail
and withstand high external pressures in many industrial applications
[89]. Due to the presence of various chemical interactions such as co-
ordination bonds, hydrogen bonding and dispersion forces that respond
incongruously towards external stresses and pressures, MOFs generally
exhibit more complicated structural properties compared to conven-
tional inorganic materials such as zeolites [90].
In the last decades, MOFs have been versatilely attempted for sto-
rage, separation and catalysis applications. Substantial efforts have also
been made in advancing MOF materials as high-performance poly-
crystalline MOF membranes [91]. Particularly, ZIF-8 membrane, a
subclass of zeolitic imidazolate framework (ZIF) MOFs, has been re-
ported for excellent hydrogen separation and organophilic pervapora-
tion owing to their ultra-small pore size of 0.34 nm and super-
hydrophobicity rendered by the methyl on the linker [92–94]. For
membrane fabrication, as the complete continuity and defect free fea-
tures are the important factors that lead to high performance MOFs
membrane, MOFs are normally grown on inorganic or organic sub-
strates to form continuous membranes. The physicochemical properties
of the substrates play an important role in dictating the quality of
crystal heterogeneous growth during the formation of continuous MOF
membranes. As such, substrates are usually subjected to physical or
chemical modification to improve the heterogeneous nucleation sites
[95]. As MOF synthesis involves the coordination between metal ions
and organic linkers, the substrates that modified with metals and
functional groups such as eNH2 and eCOOH are particularly favour-
able for MOF growth as they can serve as covalent linkers between the
MOF layer and substrates [96–98]. The synthesis of MOF membranes on
different substrates involves different procedures. In a broader term,
solvothermal or hydrothermal, interfacial synthesis and step-by-step or
layer by layer liquid phase epitaxy have been commonly applied for the
synthesis of the continuous MOF membranes [91]. Among these ap-
proaches, solvothermal or hydrothermal which can be performed
through seeded or in-situ growth demonstrates the greatest applic-
ability where almost all of the reported MOF membranes can be ob-
tained through this synthesis route. On the other hand, inspired by the
typically used interfacial polymerization to produce polyamide-based
thin film composite (TFC) for reverse osmosis or forward osmosis ap-
plications, interfacial synthesis method has been established as a new
method to prepare continuous MOF membranes. Despite the limited
application of interfacial synthesis, with intrinsically hybrid nature of
MOFs that allows the self-completing growth of thin MOF layers, this
approach presents high scalability where it can be directly used to form
MOF films on the membrane that is installed into a module [99].
Unlike zeolite membranes which require high temperature sintering
process for surfactant removal to obtain the desired pore structure, the
activation for MOF membranes can be performed at a lower tempera-
ture. Hence, MOF membranes can be feasibly supported on a polymer
substrate [100,101]. Compared to inorganic substance, polymer sub-
strates are cheaper and possess high processing ability. Large mem-
brane area, which is typically up to 50 cm2/cm3, can be obtained from
hollow fiber polymer membrane configuration for practical industrial
separation application [91]. Moreover, the organic linkers of MOFs can
establish good interaction with the polymer phase without the forma-
tion of microgaps, which often cause losses in selectivity [102]. Gen-
erally, the MOF seeds are first anchored on the polymer substrate and
followed by the growth of MOF framework on the support to form thin
films [103]. Recently, Martin et al. have shown that continuous defect-
free ZIF-8 thin films can be grown and anchored on the outer surface of
porous polymeric hollow fiber substrate via continuous flow synthesis
using water as solvent [104]. Fig. 3(a) shows the general synthesis
method of continuous MOF-membranes whereas Fig. 3(b) and (c) il-
lustrate the scanning electron microscope (SEM) images of the MOF-
membranes formed on polymeric and ceramic substrate, respectively
[91,100,105].
Hu et al. performed the first computational study to explore the
potential of hydrophobic ZIF-8 membrane for desalination [106]. The
65
Desalination 434 (2018) 60–80
molecular dynamic (MD) simulation indicated that ZIF-8 possessed the
desired intrinsic porosity to allow the permeation of water molecules,
but hindered the passage of Na+ and Cl− ions. The mechanism in-
volved also suggested that the transport of water is not highly collective
due to the presence of alternating cage-window-cage shaped pores in
ZIF-8. However, due to the dissimilarity in their size, Na+ and Cl− ions
distributed at different interfacial region in the ZIF-8 membranes where
the larger Cl− ions encounter stronger steric repulsion within the pores
and located mainly in the centers of large cavities. Benefitting from the
aperture size of 6.0 Å, Zr-MOF UiO-66 can be a promising candidate for
desalination [107]. It is expected that the inorganic membranes con-
structed from UiO-66 would realize a high selectivity towards water
molecules over hydrated ions on the basis of size exclusion. The recent
assessment by Duke et al. has revealed an important shortcoming of
ZIF-membrane [108]. Despite the substantial permeation demonstrated
by the MOF membrane, it was found that the release of Zn from the
framework upon the contact with seawater has compromised the ef-
fectiveness of selective pores and eventually resulted in unsatisfactory
salt rejection. In view of the effect of seawater on the structural in-
tegrity of ZIF-8 membranes, more efforts are required in this field to
develop well intergrown and robust membranes for practical seawater
desalination.
2.2. Carbon-based membranes
2.2.1. Carbon nanotubes membranes
CNT has been recognized as an enabling innovative technology to
address the current water shortage and water pollution problems. As
one of the members of the fullerene family, CNTs are structurally
composed of cylindrical graphite sheets that are rolled up into a
seamless tube like structure with diameter of the nanometer order and
appearance of lattice fencing. Depending on the layers of graphene
shells, CNTs can be further classified as single-walled carbon nanotubes
(SWCNTs), double-walled carbon nanotubes (DWCNTs) and multi-
walled carbon nanotubes (MWCNTs). The properties of the nanotubes
are greatly associated to their atomic arrangement (chirality), mor-
phology (defects formation) as well as nanotube diameter and length.
The science and technology development of the synthesis and char-
acterizations of CNTs have been comprehensively reviewed [109–111].
Based on the tunable properties, the rational design and manipulation
of CNT allow it to be feasibly utilized as adsorbents, catalyst or mem-
brane to offer exciting possibilities in the field of desalination and
wastewater treatment [112–116]. Some of the strong merits that pro-
mote the application of CNTs for water purification include high surface
area, antimicrobial activity, ultrafast water flux compared to other
porous materials of comparable size as well as their attractive tunable
pore size, surface chemistry and electrical conductivity.
Development of CNT membrane is an emerging branch of mem-
brane science that holds great potential to heighten and revolutionize
desalination and wastewater treatment. In general, for water purifica-
tion applications, CNTs can be configured into standalone CNT mem-
branes or incorporated into polymeric matrix to overcome the under-
lying trade-off effects observed in most of the conventionally polymeric
membranes. The special interest for the construction of CNT mem-
branes lie in the ability of the compact and dense CNT network to
provide exceptional water flux and the availability of the tips or tube
openings for facile functionalization [114]. Ideally, a CNT membrane
should constitute of well-graphitized CNT structure with uniform nano-
pores that are evenly distributed on the membrane surface. The inner
diameter of the CNT should be precisely controlled within a very
narrow range to ensure the performance of the CNT membranes [117].
In fact, the performance of CNT membrane is not only gauged by the
separation efficiency in terms of water flux and salt (or ion) rejection,
but is also based on its capability to offer synergetic antimicrobial
properties to mitigate membrane biofouling, chemical resistance to
withstand harsh filtration environment and also compelling mechanical
P.S. Goh, A.F. Ismail
strength for practical pressure driven separation processes. The CNT
membrane has been commonly synthesized by CNTs that aligned within
the perpendicular supportive fillers such as epoxy and silicon nitride
that are impermeable to water. Of all of the synthesis methods, che-
mical vapour deposition (CVD) has been proven as the most promising
approach to produce aligned CNT arrays [118]. Plasma enhanced-CVD
(PE-CVD) is one of the classical CVD methods which applies an electric
field to provoke the alignment of CNTs array in parallel to the electric
field. The CNT membrane filler which mainly acts as reinforcer can be
introduced through gas-filling or monomer infiltration. The former al-
lows the small gas molecules to efficiently fill the interstitial space
between CNTs but it involves complicated filling procedure. On the
other hand, the simpler liquid filling method is less efficient due to the
larger size and viscous flow of the polymer substrate. Very recently, Lee
and Park fabricated a highly densified vertically aligned CNT mem-
brane by the combination evaporation of ethanol and mold pressing
[119]. Ethanol plays a crucial role as the densification agent and an
inducer to infiltrate the urethane monomer within the interstitial space
between the nanotubes. This feasible technique has resulted in the CNT
membrane with pore density of 3.0 × 1012 pore/cm2 and average pore
size of 4.1 nm. Recently, facile techniques to transfer CNT array to
various types of substrates through the oxidative dissolution using weak
acid have been reported [120,121].
Since the last two decades, bountiful of studies have been under-
taken to investigate the fluid transport behavior and mechanism of CNT
[122]. The fast and frictionless fluid transport of CNT is mainly at-
tributed to the smooth and hydrophobic nonpolar wall of CNT hollow
structures. At the water-CNT interface, formation of ordered hydrogen
bonds introduces a vapour phase barrier between the channel inner
walls and the chain of water molecules, hence allowing the resistant-
free passage of water molecules [123]. Molecular ordering takes place
within the nanotubes has also been proposed as the reason for the fast
transport. With the increasing densification, more CNT wall surfaces are
available for water flow, thereby increasing the overall velocity [124].
This unprecedentedly found feature makes them a suitable candidate
for the development of high flux and low energy membrane. The salt
ion rejection of CNT membrane mainly depends on two main factors,
i.e. the inner diameter and the surface charge of the nanotubes. The
computational study conducted by Thomas and Corry suggested that
the ideal diameter of CNTs for high permeability and salt rejection for
desalination application was around 1.1 nm [125]. The opening and
pore diameter of CNT can be tailored to embody energy barriers at the
channel entries for salt ions rejections while allowing water to pass
through the hollows [126]. The ‘gate keeping’ feature can also be
66
Desalination 434 (2018) 60–80
Fig. 3. (a) The common synthesis scheme for con-
tinuous MOF membranes [91]. The cross sectional
images of (b) ZIF-8 supported on polymeric poly-
acrylonitrite support [100] and (c) MOF-199 sup-
ported on ceramic substrate of alumina oxide [105].
imparted to the CNT membrane for size-selective separation of multiple
molecules or ions by grafting adaptive and charged functional groups at
the tube ends. Suitably functionalized CNT membranes can favourably
exhibit voltage-gated transport [127]. Several groups have also re-
ported the electrically controlled fluid flow of CNT [128,129]. The
findings showed that preferred molecular ordering can be manipulated
by applying axial electric field where a spatially patterned electric field
is used to reduce the tube entrance effects in order to increase the flow
velocity [130].
It has been pointed out that, high flow rates in CNT membranes
cannot be solely attributed to the interactions of water with CNT walls
because high external pressure at the CNT entrance and exit is required
for water molecules to pass through the inner pores of pristine CNTs
with a hydrophobic surface [131]. Accordingly, hydrophilic surface
modification has been performed to reduce the resistance at the en-
trance and exit of the pores of hydrophobic CNT [132]. Oxygen etching
has also been applied to open the CNT fullerene caps to create the
passage of water through the inner pores of the CNTs. Despite the in-
troduction of some defects and oxygen-containing functional groups at
the CNT tips, the concerted effects of cap opening through etching and
hydrophilicity improvement using pyrenebutyric acid treatment have
led to a significantly increased water permeability by two fold, which
was close to 30,000 L m− 2 h− 1 bar− 1 [133]. As it is also acknowl-
edged that hydrophilic functionalization of CNT membrane may result
in the change of nanoscale environment, the mechanical and electrical
smoothness of the interior walls must be carefully retained to avoid the
disruption of the remarkable fluid flow properties of the nanotubes
[134]. Salt removal by adsorption rather than rejection has also been
demonstrated using ultralong CNT membrane treated with plasma
[135]. The ultrahigh adsorption capacity was attributed to the in-
tentionally formed defective sites and amorphous network through
plasma-mediated conversion of the outer layers of the CNTs. The pre-
sence of eCOOH and eOH functional groups on the plasma treated CNT
membrane has greatly enhance the surface hydrophilicity and ion-
binding properties. As a result, the desalination of the CNT membranes
could be barely driven by free energy of adsorption and only a small
pressure drop was required to sustain water flux and ensure fast con-
vection of salt to the UCNTs.
2.2.2. Graphene membranes
Graphene, an allotrope of carbon that consists of sp2-bonded carbon
atoms in a hexagonal honeycomb lattice, is the backbone for a new class
of highly permeable and selective membrane materials for fluid se-
paration processes [136–138]. Graphene material has been recognized
P.S. Goh, A.F. Ismail
as the new generation of RO membranes as it is known to be stronger,
thinner and more chemically robust and ion-selective than the poly-
amide active layers in TFC RO membranes [139]. As the flux across a
membrane in known to inversely proportional to the membrane's
thickness, graphene nanosheet that is bestowed with mono-atomic
thickness and two-dimensional structure membranes offer a great pro-
mise for high flux and energy efficient separation [140]. Due to the
impermeability of all atoms and molecules across the tightly packed
two-dimensional array carbon atoms in pristine graphene, nanoscale
defects must be intentionally generated to render permeability and
molecular selectivity in the material [141]. The top-down and bottom-
up synthesis approaches of nanoporous graphene (NPG) have been re-
viewed by Yuan et al. [142]. In brief, the top-down synthesis involves
processes such as chemical reduction and electrochemical synthesis to
obtain graphene with good yield whereas bottom-up method focuses on
the growth of graphene based on the chemical reaction of organic and
small molecules on a wide range of substrates [143].
A NPG membrane with high flux and exceptional molecular sieving
properties can only be realized through precise pores size formation and
with sufficiently high density of pores distributing over the macroscopic
areas of graphene. Commonly, oxidative etching processes such as high-
temperature atmospheric oxygen, hydrogen plasma and ozone treat-
ment under ultraviolet light have been commonly applied to generate
subnanometer pores on the graphene structure [144–146]. O'Hern et al.
reported the pore creation by controlled ion bombardment followed by
chemical oxidation of the nucleated defects [147]. The bombardment
by gallium ions in the graphene lattice generated reactive defect sites
that grew into pores which were terminated with negatively charged
functional groups upon the acidic oxidative etching. It should be noted
that, knocking out carbon atoms from graphene for pore creation in a
highly ordered manner still presents a great challenge to the real ap-
plication of NPG membranes. Albeit the capability of the above-
mentioned treatments to create nanopores with desired sizes, it is still
generally difficult to control the pore size distribution.
The ions or molecular selectivity of NPG is attained through the
molecular size exclusion effects rendered by the pores created on the
lattice. Compared to the state-of-the-art polymeric membranes, tre-
mendous improvements in gas, water, and water vapour permeances
have been reported for NPG. For instance, in a filtration process that
mimicking pervaporation desalination, Celebi et al. showed that the
free-standing single-layer graphene membranes with controlled pore
size < 10 nm could achieve water permeability up to 10− 9 mol
mm− 2 s− 1 Pa− 1, owing the subnanometre-sized droplet evaporation at
the vapour/liquid interface [148]. To date, MD has been extensively
used to provide insights into the graphene lattice and pore properties,
mechanisms of nanoconfined water transport phenomena in atomically
thick NPG membranes, structural strength and mechanical integrity of
the NPG under high hydraulic pressure [139,149–151]. Through their
computational work, Gai et al. have evidenced that fluorinated NPG FO
membranes with pore diameter 1.17 nm and porosity of 10% exhibited
water flux that was 1.8 × 104 times greater than that of a typical cel-
lulose triacetate membrane, without compromising the salt rejection
[152]. Cohen-Tanugi and Grossman also pointed out that the hydro-
philic functional groups that were introduced at the edges of graphene
pores served as the main factor that contributed to the high water flux.
However, the salt rejection might be compromised due to the ability of
these functional groups to substitute for water molecules in the ion
hydration shell [151]. While computational work is more prevailing,
experimental studies have also initiated to explore the potential of
graphene membrane in desalination. The proof-of-concept study re-
ported by Surwade et al. has verified that the NPG etched by oxygen
plasma could exhibit salt rejection rate of nearly 100% thus can be an
appropriate candidate for membrane distillation and RO based on the
water flux that was even higher than that of predicted from molecular
dynamics simulations for similar membrane size pores [153].
It is well agreed that, despite the breakthroughs and exciting
67
Desalination 434 (2018) 60–80
potential of NGS for ion separation, the achievement was mainly at-
tained through molecular dynamic simulations. The experimental at-
tempts are still limited as the synthesis of large-area single-crystal na-
noporous membranes with reproducible quality and high mechanical
strength still remains as a challenging task. Moreover, the precise
control of the pore size in NGS also represents a tough technical issue
due to the immature pore creation techniques. Compared to graphene
nanosheets, GO demonstrates greater potential in membrane science
due to its facile and large-scale production in solution [154]. GO, in-
cluding chemically converted graphene nanosheets, is commonly fea-
tured by the several oxygen-containing groups (epoxy, hydroxyl and
carboxyl groups) that decorate at its basal planes and edges [155].
Upon the ionization of these functional groups in aqueous medium,
highly negatively charged surface is formed to introduce strong elec-
trostatic repulsion between the GO sheets. Drop cast [156,157], spray
coating [158] and vacuum filtration [159,160] are the typically used
methods to fabricate GO membranes. Recently, Akbari et al. reported
the preparation of shear-aligned GO membrane by taking the advantage
of the unique discotic nematic crystal structure of GO with non-New-
tonian flow characteristics [161]. Compared to the aforementioned
techniques, this approach allows the large scale production of GO
membrane in a rapid single step. In general, during the formation of
membrane, the individual GO sheets are assembled and interlocked in a
parallel manner by the strong interlayer hydrogen bonds between GO
sheets to form robust GO membranes with sufficiently high strength
[155,162].
The adjacent interlayer distance of GO nanosheets can be effectively
enlarged from 0.34 nm to 0.65 nm through oxidation and exfoliation of
graphite [163]. The laminated 2D nanochannels and the wrinkled in-
terlayer space throughout the GO membrane can provide passageway to
water while blocking other species that larger than the space of the
adjacent GO nanosheets. Lamellar GO membranes (Fig. 4(a) and (b))
which fabricated from the collection micrometre-sized GO sheets to
form interlocked layered structure, are endowed with ideal character-
istics for nanoscale filtration applications [158]. These compelling
properties include high surface hydrophilicity, mechanical strength and
flexibility. Particularly, tunable nanochannels within lamellar GO
membranes offer a versatile approach for controlled passages of mole-
cules and ions [159]. It has been evidenced that the laminated free-
standing GO membranes can selectively allow water vapour to
permeate through the limited capillary channels between graphene
laminates at > 10 orders of magnitude faster than He [158]. The ul-
tralow friction of the hydrophobic graphene wall has been ascribed for
this fast water transport. As shown in Fig. 4(c), the capillary-like
pressure created within the network of graphene nanocapillaries pro-
vided a flow to maintain the wettability of the external GO surface to
limit the permeability by surface evaporation. The selective transpor-
tation of ions through the fully wetted GO film via diffusion has also
been observed in other studies [164–166]. Apart from size exclusion
mechanisms, it is also hypothesized that the oxygen-containing func-
tional groups present on the surfaces and at the edges of GO sheets can
impart electrostatic attractions and chemical interactions with the hy-
drated ions, thus simultaneously contribute to the selective penetration
of ions across GO membranes. The potential of GO membrane for NF
has been first unleashed through the fabrication of thermally corru-
gated GO membranes [167]. The corrugation helped to maintain the
multilayered graphene sheets from restacking into graphite to ensure
the readily accessibility of high specific surface area individual sheets.
The nanochannels formed by the microscopic corrugated GO wrinkles
have provided high permeance of 45 L m− 2 h− 1 bar− 1.
3. Inorganic membranes for desalination
Zhou et al. prepared a dense and phase-pure FAU desalination
membrane on a porous α-Al2O3 support using 3-aminopropyltriethox-
ysilane as an anchoring molecular linker [77]. At 90 °C and 3.5 wt%
P.S. Goh, A.F. Ismail
seawater, the FAU membrane demonstrated water flux of
5.64 kg m− 2 h− 1 and salt rejection at high as 99.8%. The prolonged
seeding-free synthesis duration, which was up to 20 h, has resulted in
the formation of thicker and denser FAU membrane which has even-
tually contributed to the increase of ion rejection in pervaporation
desalination. However, decrease in water flux was also observed due to
the greater permeation resistance. Additionally, it was also noticed that,
despite the relatively larger pore size of FAU compared to other zeo-
lites, fouling tends to occur when the channels and openings of the
zeolites were accumulated by the salt ions where the mass transfer
resistance increased. Another unfavourable condition that resulted in
the decrease of water flux was the partial ion exchange of Na+ in the
zeolite membrane by Ca2 + and/or Mg2 + with the increased operating
duration. Using phase-inversion tape casting method as a forming step,
alumina planar membrane has been prepared for direct contact mem-
brane distillation (DCMD) seawater desalination [32]. The sintered
alumina wafers were further grafted with FAS to tune the membrane
surface from hydrophilic to hydrophobic. Due to the low resistance of
support layer and the uniform small pores of the separation layer, the
FAS-modified ceramic membrane exhibited high porosity of 59% and
promising gas/water permeance. As a result, excellent salt rejection up
to 99.5% with maximum water flux of 19.1 L m− 2 h− 1 were achieved.
The flux reported in this study was comparable with the flux observed
in most of the contemporary polymer membranes.
Inorganic MMMs that are derived from carbon molecular sieve
(CMS) and α-alumina have been prepared through vacuum-assisted
impregnation for pervaporation desalination [168]. Upon the carboni-
zation of phenolic resin which act as the organic precursor, CMS
structures were formed within the pores of the alumina substrate, with
the homogeneous coverage of impregnated carbon around α-alumina
particles as shown in Fig. 5(a) and (b), to introduce preferential per-
colation pathways with low resistance to water diffusion. It was pro-
posed that, unlike hydrophilic silica and zeolite membranes, the carbon
structures repelled the hydrated ions and reduced the salt concentration
on the membrane surface, instead of retaining the ions. The rejection
mechanism has contributed to the promising salt rejections of above
93%. Based on Fig. 5(c), an impressively high water fluxes of
25 kg m− 2 h− 1 (at 75 °C) was achieved owing to the greatly reduced
thickness of CMS-Al2O3 membrane. The water flux was found to
68
Desalination 434 (2018) 60–80
Fig. 4. (a) Laminated GO membrane produced by
spray coated method, (b) cross section image
shows the laminated structure of the GO mem-
brane, (c) the schematic illustration of permeation
through the GO capillary networks and (d) per-
meability of GO membrane with respect to water
and various small molecules [158].
increase as a function of the feed temperature but the increasing feed
salt concentration did not result in significant water flux change
through the membrane.
The micro-structured surface formed by MOF crystals has allowed
the formation of superhydrophobic membranes for seawater desalina-
tion through vacuum membrane distillation (VMD). The nature-mi-
metic MOF membranes developed by Zuo and Chung involved two
primary synthesis processes, i.e. i) the double-growth of MOF functio-
nalized surface on alumina tube supports via the reaction between
alumina membrane and 2-aminoterepthalic organic linker to form the
NH2-MIL-53(Al) framework and followed by ii) the growth of hydro-
phobic floss by introducing perfluoro molecules onto the MOF surface
to lower the surface energy [169]. The optimized MOF membrane
prepared from 1 h of secondary growth time exhibited the flux of
32.3 L m− 2 h− 1 at 60 °C feed temperature. The superior flux obtained
in the VMD was attributed to the controlled microstructure of MOF
crystals and the presence of hydrophobic floss growth for better wetting
resistance. The development of a continuous Zr-MOF UiO-66 poly-
crystalline membrane supported on a predesigned porous alumina
hollow fiber for pressure driven desalination has also been reported
[107]. Under the transmembrane pressure of 10 bar, the membranes
exhibited high multivalent ion rejection of 86.3%, 98% and 99.3% for
Ca2 +, Mg2 + and Al3 +, respectively with moderate flux of
1.4 L m− 2 h− 1. The excellent divalent and trivalent ion rejection was
primarily due to the size exclusion effect rendered by the aperture size
of UiO-66. Owing to the exceptional chemical stability of the UiO-66
material, no discernible deterioration of membrane performance was
observed during the 170 h test. This observation indicated the negli-
gible damage of the crystal structure and grain boundaries. However, in
this study, poor rejection of only around 45% was obtained for Cl−,
Na+ and K+ monovalent ions with hydrated size ranging from 6.6 to
7.2 Å. Despite the smaller aperture size of UiO compared to these
monovalent ions, the non-selective passage across the MOF membranes
might be due to the missing-ligand defects in the UiO-66 crystals or the
existence of UiO-66 ligand dynamics as the coordination mode of the
carboxylate groups might change from edge-bridging to monodentate.
The desalination performance of a vertically aligned MWCNT
membrane with pore diameter of 8 nm was studied as a function of its
array density. The separation performance of the polydimethylsiloxane
P.S. Goh, A.F. Ismail
(PDMS) filled CNT membrane was governed by the charge-based fil-
tering mechanism where the electrical, surface roughness and surface
charges of PDMS have strong influences on the ion transportation
through CNTs. As the PDMS surface is typically characterized by ne-
gative charges, the Na+ ions are trapped on the PDMS surface and
resulted in salt rejection ability. While the salt rejection is almost in-
dependent of the CNT density, the permeability CNT membranes has
significant increased with the increasing density due to the availability
of additional small volumes between the CNT walls for water flowing.
With CNT density increased up to 1011 tubes cm− 2, a permeance of
1203 L m− 2 h− 1 bar− 1 and salt rejection exceeding 96.5% were ex-
perimentally achieved. Fan et al. prepared suprhydrophobic hollow
fiber CNT membranes using wet spinning technique followed by
fluorination modification for DCMD [170]. As shown in Fig. 6(a), the
sandwich and interconnected mesh structures of the CNT membrane
provided high porosity of 92%. As a consequence, the mass transport
resistance can be greatly suppressed to result in a high vapour per-
meation flux. It was found that the rapid sorption/desorption behavior
69
Desalination 434 (2018) 60–80
Fig. 5. (a) SEM cross section and (b) schematic illustration
shows the formation of CMS structures within the alumina
substrate, (c) water flux and salt rejection of 0.3–3.5 wt%
feed NaCl concentration at varying temperatures
(black = 75, red = 50 and blue = 25 °C) [168]. (For in-
terpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
Fig. 6. (a) The sandwich and mesh structure of CNT hollow
fiber membrane, (b) normalized flux under open circuit, ne-
gative polarization and positive polarization for 36 h opera-
tion and (c) schematic mechanism of electrochemically as-
sisted antifouling of CNT membranes towards NOM [170].
of CNT facilitated the transportation of water vapour molecules via
surface diffusion which in turn increased the overall vapour transport.
Owing to these characteristics, as shown in Fig. 6(b), the flux of CNT
hollow fiber membrane was 30 kg m− 2 h− 1, which was 1.5–2 fold
greater than that of polyvinylidene fluoride (PVDF) and polypropylene
(PP) hollow fiber membranes. The high electroconductivity of
98 S m− 1 allowed the membrane to perform desalination under elec-
trochemical assistance to further improve the antifouling ability. It was
suggested that under negative polarization with voltage of −0.5 V, the
CNT membrane exhibited a stable flux of 30 kg m− 2 h− 1, which re-
presented 20% improvement compared to the one operated under open
circuit. This finding suggested that electrostatic repulsion existed be-
tween the negatively polarized CNT membrane and negatively charged
foulant such as natural organic matter (NOM), as illustrated in Fig. 6(c),
thus contributed to the enhanced antifouling feature.
P.S. Goh, A.F. Ismail
4. Inorganic membranes for wastewater treatment
4.1. Oily wastewater treatment
Owing to the desired anti-fouling properties and chemical stability,
inorganic membranes have been favourably used for the treatment of
oily wastewater [171–179]. The comparative study based on several
types of commonly used metal oxide ceramic membranes indicated that
zirconia membranes could provide slightly higher flux than alumina
and titania membranes [180]. Additionally, membranes with pore sizes
of 0.1 μm could offer the most promising oil separation in term of op-
timized flux and permeate quality [181]. The anti-fouling properties
towards the deposition of oil droplet can be enhanced through the
surface roughness control of the ceramic membrane [173]. Zhong et al.
have demonstrated that controllable surface roughness can be achieved
by manipulating the templates particle size [164]. This method served
as an alternative to the more commonly applied polishing method
which suffers from inhomogeneity of morphology [182]. Though the
synthesis scheme shown in Fig. 7(a), the surface roughness of alumina
membrane increased with the increasing particle size of poly(methyl
methacrylate) template as evidenced in the atomic force microscopy
(AFM) images in Fig. 7(b). Despite the imperceptible effects on the pure
water flux and oil rejection, the smoother membrane surface has re-
sulted in higher and more stable flux. As oil droplets are preferentially
accumulated in the valleys structures of the rough membranes as illu-
strated in Fig. 7(d), smoother membrane surface can minimize the
formation of fouling layer to achieve higher steady flux.
UF membrane based on low cost multilayer γ-Al2O3 ceramic
70
Desalination 434 (2018) 60–80
Fig. 7. (a) Schematic illustration of controlled surface
roughness alumina membrane fabrication, (b) AFM topo-
graphy indicated that surface roughness increased with the
increasing PMMA particle size from 0.64 to 176.10 μm, (c)
the effect of surface roughness on the decline of flux where
the highest steady flux was achieved with the smoothest
membrane and (d) illustration shows that the rougher
surface unfavourably allowed the deposition of oil droplet
on the membrane surface [173].
membrane has been investigated as an alternative for pretreatment of
oily wastewater [172]. The thin top alumina layer which was fabricated
using boehmite sol on an α-alumina support via dip-coating technique
exhibited homogeneity and good adhesion with no cracks or pinholes
mainly due to the similar properties of both alumina support and thin
layers. The multilayer γ-Al2O3 ceramic membranes are efficient for
treatment of petroleum refinery wastewater to meet the discharge
standard of 10 mg/L where the total suspended solids as well as the oil
and grease content are reduced by 86% and 84% respectively. In an-
other recent study, TiO2 membrane supported on mullite hollow fiber
produced from low cost industrial solid waste coal fly ash has been
developed via dip-coating method for oil in water emulsion treatment
[174]. In the composite ceramic membrane, the titania thin layer has
increased the surface hydroxyl groups, thus enhancing the membrane
hydrophilicity to repel oil droplets from adhering onto it. It is known
that hydrophilic membrane pores have high capillary repulsing force to
prevent oil droplets from transporting across and consequently hinder
surface adsorption and reduce fouling tendency. Similar hydrophilic
modification of ceramic membrane have also been performed using
nanomaterials [59,183]. Chang et al. performed nano-TiO2 coating by
an in-situ precipitation method to uniformly distribute the nano-
particles onto the surface of alumina MF membrane [183] meanwhile
Hu et al. modified the commercial alumina membrane with GO through
transfer via vacuum method [59]. The attachment of GO coating on the
alumina membrane pore surface has resulted in the alteration of surface
hydrophilic and charge and consequently accelerating the water per-
meability across the membrane pores. High flux of
667 L m− 2 h− 1 bar− 1 with rejection of 98.7% has been achieved.
P.S. Goh, A.F. Ismail
Fig. 8. (a) Cross section image shows the incorporation of carbon-nanotube network (CNTN) within the pores of the zirconia ceramic matrix in the ceramic-hybrid membrane, (b) the
removing emulsified oil from water based on 3 possible mechanisms and (c) steady-state rejection and flux of the pristine membrane (PM) and CNTN-ZrO membrane (CM) for as a
function of feed concentration [176].
Standing on the synergetic effect arisen from membrane separation
and nanomaterial adsorption mechanisms, Chen et al. pioneered the
fabrication of ceramic-hybrid membrane consists of CNT network and
zirconia ceramic membranes to purify surfactant stabilized oil emulsion
[176,184]. The nanostructured carbon nanotube network (CNTN) was
grown into the pore channels of ceramic matrix through in-situ catalytic
reaction (Fig. 8(a)). As depicted in Fig. 8(b), it was proposed that three
mechanisms were involved in the removal of emulsified oil from water,
i.e. i) size-exclusion, ii) surface adsorption through interaction with
ceramic membrane and iii) multi-layer adsorption by CNT. The macro-
mesoporous ceramic membrane could reject oil molecules, leaving only
the smaller emulsified oil (< 0.5 mm) and dissolved oil to enter the
pore channels so the fouling within the pore channels could be mini-
mized. Compared to the pristine ceramic membrane, the ceramic-hy-
brid membrane demonstrated a remarkable improvement in its oil re-
jection and flux in different feed operating conditions. As shown in
Fig. 8(c) and (d), both pristine and CNTN-ZrO membrane exhibited
rejection of 100% but the flux of CNTN-ZrO (26 L m− 2 h− 1) was much
higher than that of pristine ceramic membrane (1.2 L m− 2 h− 1) at the
steady state. The higher flux was majorly attributed to the CNTs which
have significantly decreased the tendency of gel layer formation hence
greatly reduced the flow resistance. Due to the hydrophobic nature, the
attachment of surfactant can be hampered. Besides that, high surface
area CNTN also capable to adsorb smaller emulsified oil and dissolved
oil through hydrophobic-hydrophobic interaction and effectively re-
move the emulsified oil.
Zhao et al. explored the tunability of channel structures and surface
topology of self-assembly GO membrane through the intercalation of
palygorskite nanorods into adjacent GO nanosheets via vacuum-assisted
filtration [185]. Through the crosslinking and formation of stable bonds
within the GO laminate structure, the intercalated palygorskite na-
norods have desirably increased interlayer distance and structural dis-
order without affecting the stability of the GO membrane. The high
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Desalination 434 (2018) 60–80
water permeability and antifouling capacity was the synergistic effect
of the hierarchical nanostructures and excellent hydration capacity
which have furnished the membranes with favourable water passage,
high underwater superoleophobicity and low oil-adhesive water/
membrane interface. At the optimum palygorskite nanorods, the max-
imum flux of 1867 L m− 2 h− 1 was obtained owing to the enlarged
interlayer spacing. On the other hand, the hydrophilic groups on the GO
membrane surfaces induced the formation of hydration layer at the
water/membrane interfaces. This has in turn created strong repulsive
barrier for the attachment of oil droplets.
4.2. Dyes and organic waste removal
Azobenzene modified anodized alumina membrane has been de-
veloped for photo-induced rhodamine B removal [186]. Azobenzene
group grafted on anodized alumina membrane, which was synthesized
via the scheme depicted in Fig. 9(a), experienced continuous photo-
cis‑trans isomerization induced by the simultaneous UV and visible
light radiation. The intense motion act as a molecular impeller to ac-
tivate and accelerate the movement of the nearby molecules, hence
promoting the water permeation by water vapourization. As the non-
volatile dye molecules could not vapourize, the complete separation of
rhodamine B from aqueous solutions dissolving dyes was accomplished
as shown in Fig. 9(b). Such modification represents the potential of
performing solar-driven filtration (Fig. 9(c)) by applying active group-
functionalized ceramic membrane. Removal of hazardous volatile me-
thyl tert-butyl ether (MTBE) from water by vacuum pervaporation with
perfluorooctyltriethoxysilane hydrophobized titania membranes has
been reported [187]. The solvent solubility and the density of hydro-
phobic layer are found to impart important impacts on the pervapora-
tion transport and separation properties. As MTBE is one of the most
coherent solvents with the grafting molecules, high separation factor of
91 and pervaporation separation index (PSI) of 194 that equivent to
P.S. Goh, A.F. Ismail
Fig. 9. (a) Preparation processes of azobenzene modified anodized alumina membranes, (b) the permeated water from rhodamine B solution through the azobenzene modified membrane
during the photo-induced filtration and (c) the potential application of solar-driven filtration set up based on the azobenzene modified anodized alumina membrane [186].
removal efficiency of 98.5% were achieved. The permeate flux of MTBE
and concentration of MTBE in feed were contributed by the loose hy-
drophobic brush attached on the titania membrane. However, due to
the conformation change of the hydrophobic chains from tangled to
straightened upon the contact with water and organic compounds,
decrease of water flux was observed in the water–MTBE mixture during
the pervaporation.
Li et al. fabricated ZIF-8 from zinc nitrate precursor and 2-methy-
limidazole linker through interfacial synthesis method on a poly-
ethersulfone (PES) based ultrafiltration substrate. 1-Octanol with pro-
mising linker/metal source solubility was used as the linker solvent
[188]. During the growing process, the growth and self-terminated
reaction took place in a single step to form a thin layer of ZIF-8 with
thickness around 250–300 nm (Fig. 10(a)). Due to the immiscible in-
terface created by octanol, diffusion of the precursor was faster at the
remaining defects than through the preformed layer. Hence, formation
of new crystals primarily took place at the defect sites, thereby sealing
the defects. The octanol solvent also prevented the pore collapse as PES
support with longer octanol treatment duration exhibited higher per-
meance, indicating the availability of more pores for filtration. Higher
molar ratio of linker to precursor promoted the formation of denser
membranes with higher dense packing and smaller inter-particle
spaces, thus lowered the permeance and increased the rejection. As
depicted in Fig. 10(b), a dense support was more favourable to maintain
the higher ratio of 2-methylimidazole to zinc nitrate at the interface as
the transport of zinc nitrate from the bulk of the support to the interface
could be restricted at the smaller pores of the water/octanol interface.
As shown in Fig. 10(c), by increasing the molar ratio of 2-methylimi-
zaole to zinc nitrate from 1.9 to 15.9, the permeance of the resultant
ZIF-8/PES membrane decreased from 37.5 to 5.6 L m− 2 h− 1 bar− 1,
but the Rose Bengal rejection was increased to 98%. The findings of this
study showed that ZIF-8 membranes with less defects can be fabricated
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Desalination 434 (2018) 60–80
with higher linker to precursor mole ratios of and denser support.
NF membrane with reduced graphene oxide (rGO) intercalated CNT
network supported on a macroporous anodic alumina support has been
investigated for humic acid removal [189]. The dispersion of CNTs
using block copolymers prior to the incorporation has resulted in the
flat and defect free membrane surface. The intercalation of 1D CNT and
2D graphene sheets promoted the formation of a continuous 3D na-
nostructure that act as mass transfer channels. Thereby, high perme-
ability of 20 L m− 2 h− 1 bar− 1 and rejection of 99% fulvic acid were
observed with the uniform network formed. Owing to the smooth and
hydrophilic membrane surface, the rGO-CNTs NF membranes pre-
vented the adsorption of fulvic acid onto the membrane surface, hence
exhibited promising antifouling properties. Nano-strand-channelled GO
UF membranes with nanochannels of 3–5 nm diameter size have been
developed through vacuum filtration for Evans Blue (EB) removal
[190]. Negatively charged carboxyl groups have been abundantly
found on the edges of the GO sheets and on the entrance of the na-
nochannels to facilitate the water access into the nanochannels hence
resulted in permeance of 695 L m− 2 h− 1 bar− 1. Another main reason
for the enhanced water flow was the frictionless and boundary slip
properties in the nanoconfined hydrophobic channels found in the
pristine graphene regions in the GO membranes. The GO nanochannels
with uniform size distribution have contributed to 83% of size-depen-
dent rejection of EB.
4.3. Heavy metal and radioactive ions removal
Recent studies revealed that heavy metal cations removal can be
performed using charged membranes where the separation is mainly
achieved based on the formation of water-soluble positively-charged
hydrolyzed species adsorbed onto the charged membrane surface
[191]. Based on the abundancy of surface reactive functional groups,
P.S. Goh, A.F. Ismail
Fig. 10. (a) Cross section image of a ZIF-8/PES membrane showed the ZIF-8 layer of 250–300 nm, (b) schematic diagram of the support effect on the transport of zinc nitrate from the
bulk of the support to the interface, (c) influence of zinc nitrate concentration in the aqueous phase (d) influence of 2-methylimidazole concentration in the organic phase [188].
silica membranes have been commonly used for heavy metal ions re-
moval. Divalent heavy metal such as Pb2 +, Cu2 +, and Cd2 + ions have
been effectively removed by silica ceramic membrane at alkaline aqu-
eous environment [192]. Removal efficiency of > 97% was attributed
to the precipitation of surface ion to form insoluble metal hydroxides at
the elevating pH during the filtration. Upon the contact with the pores
with adsorptive site during the filtration process, the positively charged
heavy metal ions were adsorbed on the surface active OH− functional
groups, independent on the size-exclusion mechanism. You et al. have
developed nanoporous silica thin-film inorganic (TFI) membrane via
tetraethylorthosilicate-driven sol-gel process to remove divalent heavy
metal ions through FO process [193]. Effective rejection up to 94% at
slightly acidic 200 ppm feed concentration was achieved based on the
charge-interaction between the heavy metal ions and silica-made pore
walls. Credited to the unique quasi-symmetry structure and the hy-
drophilicity of silica matrix, the internal concentration polymerization
has been greatly minimized for effective water transport to yield a high
water flux of 69.0 L m− 2 h− 1 using 2.0 M NaCl draw solution.
Several types of inorganic membranes have been examined for
chromium removal [194]. Kumar et al. fabricated an analcime-C/
ceramic composite membrane for chromium removal by repeatedly
coating analcime-C on the ceramic support through in situ crystal-
lization technique [195]. The repeated multiple coating up to 3 layers
has ensured good adhesion of zeolite particles where the ceramic pores
at the support were well roofed with a dense film of zeolite. When
subjected to Cr4 + removal through UF, the maximum rejection of 84%
was achieved by the tri-layer coated membrane with Cr4 + concentra-
tion of 250 ppm. As the surface charge of the zeolite membrane can be
manipulated under different solution pH and the oxidation forms of
chromium (Cr4 + and Cr3 +) are also exchangeable based on the pH of
the solution, the rejection efficiency of the zeolite membrane was en-
hanced at high pH of 11. In another similar work, zeolite/ceramic UF
composite membranes which were supported on circular shaped porous
ceramic have been used for the removal of Cr4 + from aqueous solution
in cross flow mode [196]. The porous ceramic was fabricated using clay
materials via uniaxial compaction followed by sintering process The
removal performances of MCM-41, MCM-48 and FAU zeolites were
compared based on their surface hydrophilicity, porosity and surface
73
Desalination 434 (2018) 60–80
charges. The interaction between the charged zeolite membranes and
chromium ions allowed the removal of Cr4 + from aqueous solution
particularly at higher applied pressure where the retentions of ions
within the membrane pores have resulted in the buildup of con-
centration polarization effect and convective transport was more sig-
nificant than the diffusive transport. As such, the maximum rejections
of 75, 77 and 82% were achieved using MCM-41, MCM-48 and FAU
zeolite composite membrane, respectively. Due to the greatest deposi-
tion amount on the ceramic support and hydrophilic nature, the Cr4 +
removal performance of FAU zeolite membrane has overwhelmed that
of MCM-41 and MCM-48.
Sklari et al. developed a hybrid process using two sequentially ar-
ranged ceramic membrane modules to perform As3 +/As5 + ions re-
moval [197]. The first alumina membrane module served as a contactor
to supply ozone from the external surface to the inner water stream in
order to oxidize As3 + to As5 +. Functionalization using tri-
chloromethylsilane was conducted to render hydrophobicity on the
alumina surface and facilitate the flow of ozone stream. In the second
module, the alumina UF membrane was modified by the in situ gen-
eration of Fe3O4 nanoparticles at the interior pore structure in order to
serve as adsorbent for As5 +. The careful design of the ceramic mem-
brane characteristics based on the nature of contaminant has resulted in
the complete removal of arsenic. TiO2-doped ZrO2 NF membranes
fabricated via modified colloidal sol-gel method has been utilized for
the simulation of the radioactive wastewater treatment [198]. The TiO2
doping modified the microstructure of ZrO2 membrane into finer grains
with narrower accumulated pore sizes and larger specific surfaces. The
improvement in hydrophilicity was also observed to render greater
mechanical strength and enhanced separation performance. Conse-
quently, the promising water permeability of 40 L m− 2 h− 1 bar− 1 was
obtained along with rejection of 99.6% for Co2 +, 99.2% for Sr2 + and
75.5% for Cs+.
4.4. Inorganic waste removal
Lately, MOF membranes have been investigated for water de-
fluoridation based on the high adsorption capacity towards fluoride
compared to other adsorbents. An adsorptive Zr-MOF membrane with
P.S. Goh, A.F. Ismail
high specific area of 740.28 m2/g has been reported by He et al. for
rapid removal of fluoride from aqueous solution [199]. The alumina
supported continuous polycrystalline Zr-MOFs membrane with 20 μm
thickness was fabricated through in situ solvothermal method. The
fluoride removal capability of the Zr-MOFs membrane is found de-
pending on the flow rate and initial concentration of fluoride. With
initial fluoride concentration of 5 mg/L and flow rate of 15 mL min− 1,
the Zr-MOF membrane could achieve maximum fluoride removal
ability of 5510 L m− 2. The characterizations after the adsorptive re-
moval process indicated that the surface hydroxyl groups and Zr(IV)
active sites have contributed to the fluoride adsorption where the hy-
droxyl groups bonded to Zr-MOF adsorbent could efficiently exchange
with the fluoride species. Shang et al. explored the potential of tight
TiO2 UF membrane in RO pretreatment for phosphate removal [200].
Electrostatic repulsion was identified as the dominant mechanism that
has contributed to the phosphate anion rejection, where the rejection
increased with the increasing density of surface negative charge. As
ceramic membranes with a tighter pore size and greater negative sur-
face charge density often lead to more effective rejection of the less
diffusive anions such as phosphate, the maximum phosphate rejection
of 87% was achieved in this study at pH 8.5 using the 3 kDa negatively
charged TiO2 membrane.
The capture of ammonia through pervaporation has been demon-
strated using a cobalt-doped molecular sieve silica membrane [201].
Controlled hydrothermal treatment has been performed on the silica
membrane to induce the desired membrane pore expansion the se-
lectivity of different species across the membrane pores. Owing the
molecular sieving mechanism that only favoured the passage of water,
excellent ammonia selectivity up to 60 which was 5 times more effec-
tive than that of hydrophobic polypropylene membrane could be
achieved. To deal with the material degradation issue, Yang et al. ex-
plored the use of hydrostable organosilica as the pervaporation mem-
brane material for in alkaline ammonia solution treatment [202]. At
high ammonia concentration, hydrolysis of siloxane on the silica sur-
face took place and led to the formation of silanol groups. Nevertheless,
this slight chemical change of silica only diminished some small pores
without compromising the material integrity. The main reason for the
performance deterioration at elevating ammonia concentration was the
more severe pore structure degradation occurred at the underlying
alumina supporting layer. This study highlighted the importance of
optimizing the structural properties of the ceramic membrane by con-
sidering both support and selective layer.
5. Challenges and future outlook
The promising separation performance of inorganic membranes, as
exemplified in Table 1, has evidenced the capability of inorganic
membranes for a wide range of desalination and wastewater treatment
applications. Particularly, the diverse structural and chemical varia-
bility has offered vast opportunities for the desired tuning and mod-
ulation of membranes. In the past, the relatively low acceptance of
inorganic membranes is mainly stemmed from the sheer dominance of
polymeric membranes in commercial-scaled RO processes. By virtue of
the material uniqueness demonstrated by most inorganic membranes,
their applications for desalination and wastewater treatment have been
acknowledged as an important field that can lead to many important
niche areas. Recent research into inorganic membranes for desalination
applications has been gathering pace in desalination processes such as
membrane distillation and pervaporation. The preparation of inorganic
membranes with reduced thickness such as those interlayer free
ceramic membranes and free-standing CNT and GNP membranes also
open a window of opportunities to deliver high output potable water
production for practical water processing. These highly permeable
membranes are standing at a good position to deliver material and
energy efficient treatment process with greatly reduced capital cost of
the facility. Several feasible studies have been conducted to provide
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Desalination 434 (2018) 60–80
statistically defensible aspects of the implementation of full commercial
scaled plant based on ceramic membranes [180,203]. The economic
assessment of a full scale ceramic plant for oilfield produced water
treatment suggested that, under an optimal crossflow velocity of 2.0 m/
s and water recovery rate of 95%, the cost related to operation expenses
(OPEX) and total cost are US$0.23/m3 and US$3.21/m3, respectively.
With the capacity of 1000 m3 h− 1 of produced water, the capital ex-
penditures (CAPEX) is estimated at US$7.33 [180].
The cost involved in the development of these inorganic mem-
branes, particularly those derived from nanomaterials, still remain as a
significant stumbling block for their commercial deployment. For in-
stance, despite the rapid growth and development of CNT research in
laboratory scales, the commercial applications of CNT membrane for
water treatment and desalination is still ongoing progressively but in a
rather slow pace primarily because of the high production costs of high
quality and reproducible CNTs. The recent advancement in material
synthesis may enable the large scale manufacturing of high quality
CNTs at low prices. However, the reproducibility and appropriateness
of the method, such as catalytic CVD, for the fabrication of CNT
membranes is still in doubts. It should be pointed out that, while the
earlier assessment performed by Pendergast and Hoek has indicated
that CNT and zeolite membranes might still far from commercial via-
bility due to material cost and scalability [204], a more recent esti-
mation also pointed out that the large scale fabrication of MFI-type
zeolite membranes come to US$ 2700/m2, which is double of the cost
involved in the fabrication of polymeric membranes [205]. The critical
cost related issue of conventional metal oxide-based ceramic mem-
branes is the preparation of expensive supports that made from α and γ-
alumina, TiO2, ZrO2 and glass [196]. Thanks to the constant explora-
tion in material development, current trend of research is focused on
the application of alternative inorganic membranes that synthesized
from cheaper naturally found or waste raw materials to reduce the
capital investment.
Another major challenges in inorganic membranes is the reprodu-
cibility and feasibility in a large scale synthesis. Scalable and in-
dustrially adaptable production methods are highly desired to address
this challenge. By taking zeolite membrane as an example, the im-
portant obstacle related to its industrial development is the long cal-
cination step used in the typical synthesis approach. On the other hand,
while in situ growth is known to be a challenging task due to the poor
heterogeneous nucleation site of MOF on the substrate, the additional
steps that involve seeding and substrate modification to improve the
density of the heterogeneous nucleation sites on the surface of sub-
strates and adhesion and nuclei on the substrate have complicated the
membrane synthesis process. The waste of raw materials, hence the cost
and safety, is also a common issue linked to this synthesis approach as
the MOF crystals will be formed in bulk from the mixture precursor
solution of metal ions and linker. Hence, the hydrothermal or sol-
vothermal method is always associated with the difficulty in scaling up.
In the coming future, efforts should be focused on the establishment of
more viable approaches to improve the practicability while retaining
the good quality and separation performance. Bulk synthesis methods
that can obtain a uniform, highly ordered, smooth membrane free of
cracks or intercrystal gaps need to be established to rapidly ap-
proaching commercial viability. Some recent explorations demon-
strated that the synthesis of microporous crystalline network solid thin
film based on vapour-phase deposition method and cathodic deposition
may mark a new milestone in the processing of defect free materials
[206,207]. The recent demonstrations of easily detachment of vertically
aligned CNT (VACNT) from the growth substrates to obtain a free-
standing film have opened a way for the development of large- area
CNT-based membranes for commercial applications by transferring
multiple VACNT films onto large-size membranes or substrates. Sub-
sequently, more experimental works are necessary to improve the re-
liability and maturity of the technology. Furthermore, surface mod-
ification is an attractive approach to improve the surface properties and
P.S. Goh, A.F. Ismail Desalination 434 (2018) 60–80

Table 1
Performance evaluation of different classes of inorganic membranes for desalination and wastewater treatment.

Inorganic membrane Wastewater/desalination Rejection Flux/permeability Reference

FAS grafted Al2O3 DCMD desalination 99.5% 19.1 kg m− 2 h− 1, 2.0 wt% NaCl, 80 °C [32]
γ-Al2O3 NF desalination Fe3 + = 97.1%, Al3 + = 90.9%, Mg2 + = 85.0%, 17.4 L m− 2 h− 1 bar− 1 [35]
Ca2 + = 84.1%, Na+ = 30.7%, NH4+ = 27.3%
Organosilica MD desalination 99.9% 13 kg m− 2 h− 1, 3.5 wt% NaCl, 60 °C [38]
SiO2 Pervaporation desalination 99.6% 9.5 kg m− 2 h− 1, 3.5 wt% NaCl, 22 °C [36]
SiO2 Pervaporation desalination 99.5% 6.6 kg m− 2 h− 1.3.5 wt% NaCl, 22 °C [39]
CoO-SiO2 Pervaporation desalination 99.7% 7.7 kg m− 2 h− 1, 3.5 wt% NaCl, 22 °C [40]
TiO2 Pervaporation desalination 99% 6.0 kg m− 2 h− 1.10 wt% NaCl, 75 °C [33]
CMS-Al2O3 Pervaporation desalination 93% 25 kg m− 2 h− 1, 3.5 wt% NaCl, 75 °C [168]
Clinoptilolites zeolite Pervaporation desalination Mg2 + = 99.99%, Ca2 + = 98.52%, Na+ and 2.5 kg m− 2 h− 1, 93 °C [73]
K+ > 97.5%
FAU zeolite Pervaporation desalination Na+, K+, Ca2 +, Mg2 + > 99.8% 5.64 kg m− 2 h− 1, 90 °C [77]
MFI Desalination Na+ 82% 7 L m− 2 h− 1 [82]
MFI Salined wastewater Ca2 + and Mg2 + > 90%, K+ and Na+ > 70% 6.8 × 10− 4 L m− 2 h− 1·kPa [79]
MOF-functionalized Al2O3 VMD desalination – 32.3 L m− 2 h− 1, 3.5 wt% NaCl, 90 °C [169]
tube
UiO-66 Pressure driven desalination Ca2 + = 86.3%, Mg2 + = 98. 0% Al3 + = 99.3% 0.14 L m− 2 h− 1 bar− 1 [107]
MWCNT Desalination Na+ = 96.5% 1203 L m− 2 h− 1 bar− 1
FAS-CNT DCMD desalination – 67.69 mL h− 1 [192]
γ-Al2O3 UF oil/water 84% 112.7 kg m− 2 h− 1, 5 bar [172]
Al2O3 MF oil/water 99% 450 kg m− 2 h− 1, 0.15 MPa [173]
TiO2-Mullite MF oil/water 97% (TOC) 150 L m− 2 h− 1 bar− 1 [174]
TiO2-Al2O3 MF oil/water 99.9% 320 L m− 2 h− 1 bar− 1 [183]
GO-Al2O3 MF oil/water 98.7% 667 L m− 2 h− 1 bar− 1 [59]
Palygorskite-GO UF oil/water 99.9 1867 L m− 2 h− 1 [185]
CNT-ZrO MF oil/water/surfactant 100% 26 L m− 2 h− 1 [176]
PVA-Al2O3 NF Congo red dye desalination 96% Congo red 25 L m− 2 h− 1 [66]
3% NaCl
SiO2 MB dye 80% 40 L m− 2 d− 1 [45]
FAS grafted TiO2 Pervaporation MTBE organic 98.5% – [187]
solvent removal
ZIF supported on PES NF Rose Bengal removal 85% 90 L m− 2 h− 1 bar− 1 [188]
rGO-CNT NF humic acid 99% 20 L m− 2 h− 1 bar− 1 [189]
GO UF EB dye 83% 695 L m− 2 h− 1 bar− 1 [190]
MCM-41 UF Cr4 + removal 75% 6.05 × 10− 8 m3/m2 s·kPa [196]
MCM-41-ceramic Cr4 + removal 80% 1.1007 × 105 m/s [194]
MCM-48 UF Cr4 + removal 77% 4.18 × 10− 8 m3/m2 s·kPa [196]
FAU UF Cr4 + removal 82% 6.09 × 10− 8 m3/m2 s·kPa [196]
Analcime-C UF Cr4 + removal 84% 4.53 × 10− 8 m3/m2 s·kPa [195]
TiO2 UF PO43 − 87% – [200]
SiO2 Pb2 +, Cu2 + and Cd2 + > 97% 55.27 mL h− 1 [192]
SiO2 FO Pb2 +, Cu2 +, Cd2 +, Zn2 + 94% 69 L m− 2 h− 1 [193]
Al2O3 UF As3 +/As5 + 100% 75 L m− 2 min− 1 [197]
TiO2-ZrO2 NF radioactive waste 99.6% for Co2 +, 99.2% for Sr2 + and 75.5% for Cs+ 40 L m− 2 h− 1 bar− 1 [198]
Zr-MOF Batch adsorption of fluoride – 4664 L m− 2 [199]
removal
SiO2 Ammonia Separation factor = 60 1.7 L m− 2 h− 1.75 °C [201]

render desired functionality for effective functionalization. As such, for
practical application, the scale-up, stability and reproducibility of the
functionalized inorganic membranes should also be of the main con-
cern.
It is well agreed that computational chemistry has played very
crucial role in answering questions about water transport phenomena
that are closely related to the membrane structures and functions. As
the characterizations of some nanomaterials at atomic scale are still
difficult to be performed experimentally, computational study can be an
ideal approach to provide insights into this matter. Currently, MD si-
mulation has been extensively used to investigate the structure and
orientation involved in the water passage across the membranes to
provide breakthrough findings for scientific and technological im-
provement. However, one of the most prominent weaknesses of these
nanosized materials is the substantially degraded properties resulted
from the presence of structural defects. Most defects found in mem-
brane structures have greatly thwarted their separation characteristics
in ideal form. As a result, most of the fascinating properties in term of
the strength, ion selectivity and fast water transport cannot be realized
at their maximum limit when tested experimentally. For examples,
experimentally synthesized zeolite membranes are prone to imperfect
polycrystalline formation and CNT membranes known to suffer from
the mechanical strength and water flux that are far below the predicted
value. Additionally, some contradictory findings have been reported for
the water transport mechanisms of some nanoscaled inorganics. The
inconsistency highlights the challenges in completely understanding the
transport mechanisms through the confined nanopores of the inorganic
materials. It also indicates that small changes in the surface properties
and chemistry in term of the crystal size as well as the variations in
compositions, defects, and intercrystalline mesoporosity can play key
roles in manipulating the measured water flux. Hence, more experi-
mental trials are still needed to better understand the structure and
behavior of these materials. It is also important to correlate the struc-
ture properties to the synthesis conditions, transport mechanisms and
eventually the separation performance of these inorganic membranes. It
has also been well evidenced that the mode and efficiency applications
of the abovementioned inorganic materials in water purification are
closely associated to their framework topology, shapes and perfection
of crystal structures. These variations can be feasibly achieved by the
strategic alterations in the chemical composition and synthesis condi-
tions. From material science point of view, a full understanding of the
chemical effects such as chemical composition and reaction route is

75
P.S. Goh, A.F. Ismail Desalination 434 (2018) 60–80

eminently important to guarantee the successful development of novel HDTMS hexadecyltrimethoxysilane

advanced and functional materials with desired characteristics and GO graphene oxide
structural flexibility. Hence, more efforts should be targeted on ex- DM dynamic membrane
ploring the key influential factors to control the quality of the final CA cellulose acetate
product. For instance, the crystallization pathway and particulate SBU secondary building units
properties should be well studied to have better control over the zeolite ZIF zeolitic imidazolate framework
particulate properties [208]. Similarly, the overall connectivity pattern TFC thin film composite
of the MOF building units should be focused to ensure the robustness SEM scanning electron microscope
and durability of the material [89]. MD molecular dynamic
SWCNTs single-walled carbon nanotubes
6. Concluding remarks DWCNTs double-walled carbon nanotubes
MWCNTs multi-walled carbon nanotubes
The growing needs to solve water and energy scarcity issue have CVD chemical vapour deposition
triggered tremendous efforts to cope with the problem. Currently, NPG nanoporous graphene
membrane technology based on polymeric membranes is still the DCMD direct contact membrane distillation
leading desalination and wastewater treatment technology to overcome CMS carbon molecular sieve
the global water pollution and shortage issue. In parallel with the de- VMD vacuum membrane distillation
velopments of polymeric membranes, scientists and engineers have PDMS polydimethylsiloxane
been extensively investigating the development of the more efficient PVDF polyvinylidene fluoride
membrane for sustainability production of potable water. The com- PP polypropylene
bined functionality and chemistry of inorganic materials have offered NOM natural organic matter
great opportunities to realize optimal inorganic membrane performance AFM atomic force microscopy
that is targeted for industrial applications. The relatively new class of CNTN carbon nanotube network
inorganic nanostructure has been touted as intriguing membrane ma- MTBE methyl tert-butyl ether
terials for desalination and wastewater treatment. To make significant PSI pervaporation separation index
breakthroughs that could be commercially exploited, current inorganic PES polyethersulfone
membrane science and technology has been directed towards several rGO reduced graphene oxide
crucial strategies: hierarchical design of individual or hybrid inorganic EB Evans blue
materials and molecules that enhance functionality, flux and selectivity; TFI thin-film inorganic
fabrication of thin and defect-free support or interlayer-free membrane; OPEX operation expenses
development of free standing carbon-based membranes using facile CAPEX capital expenditures
approaches; cost reduction by application of cheap raw materials and VACNT vertically aligned CNT
development of cost-effective fabrication methods. Additionally, with
more emerging ideas and strategies to improve processing techniques Acknowledgement
and minimize the defects, inorganic membranes hold the promising
potential for real-world applications. Authors would like to acknowledge the financial support obtained
In order to maximize the sustainable use of the opportunities offered from Ministry of Higher Education under HiCOE Grant (4J182, 4J196)
by the advancement made in this field, it is crucial to ensure their and Universiti Teknologi Malaysia under Research University Grant
economic competitiveness and values along their technological devel- 13H65.
opment. With the current development, inorganic membrane materials
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