Desalination 308 (2013) 214

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

Carbon nanotubes for desalination: Performance evaluation and current hurdles

P.S. Goh, A.F. Ismail , B.C. Ng
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia
Faculty of Petroleum and Renewable Energy Engineering, Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia

H I G H L I G H T S
CNTs have been utilized to heighten the performance of water desalination technology.
The smooth channel of CNTs has facilitated improved ux in desalination.
Application of CNTs in desalination is expected to lead the future direction of the realm.

a r t i c l e

i n f o

Article history:
Received 27 March 2012
Received in revised form 24 July 2012
Accepted 27 July 2012
Available online 28 August 2012
Keywords:
Desalination
Carbon nanotubes
Membrane
Electrode

a b s t r a c t
The fast-evolving world of nanotechnology captivates researchers in the state-of-the-art water desalination
technologies. Rapid development and advancement have been reected by a drastically increasing number
of scientic investigation on the manipulation of nanomaterials in various desalination technologies. With
demand rising in worldwide, the revolution of desalination technology using CNT materials to mitigate few
raised over concerns, particularly energy issues, seems a viable option. In this context, this review article intends
to provide an in-depth insight on the utilization of CNTs to heighten the performance of the available seawater
and brackish water desalination in a holistic manner. The transport properties and chemical functionalities of this
novel material to potentially facilitate excellent ux of water transport and salt rejection are outlined. Based on
the computational and experimental work done over the past decade, a detailed description on the current
knowledge relevant to the exploitation of CNTs in desalination has been highlighted. The current hurdles and
future challenges related to this technology are then addressed. With novel properties come new opportunities
for technological and commercial development. The applications of CNTs in desalination have been demonstrated and it is anticipated that applying CNTs in desalination holds very promising future prospects and will therefore lead the future direction of the realm.
2012 Elsevier B.V. All rights reserved.

Contents
1.
2.
3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Emerging nanotechnology for water desalination . . . . . . . . . . . .
Carbon nanotubes as potential materials for water desalination . . . . . .
3.1.
Water and ion transport in carbon nanotubes . . . . . . . . . . .
3.2.
Modication of carbon nanotubes for salt rejection . . . . . . . .
4.
Performance evaluation of carbon nanotube material for water desalination
4.1.
Carbon nanotube membranes . . . . . . . . . . . . . . . . . .
4.2.
Carbon nanotubes/polymer mixed matrix membrane . . . . . . .
4.3.
Carbon nanotube electrodes . . . . . . . . . . . . . . . . . . .
5.
Current hurdles and future challenges
. . . . . . . . . . . . . . . . .
6.
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Corresponding author at: Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia. Tel.: +60 7 5535592;
fax: +60 7 5581463.
E-mail address: afauzi@utm.my (A.F. Ismail).
0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2012.07.040

P.S. Goh et al. / Desalination 308 (2013) 214

1. Introduction
Water is an essential resource for life on Earth and therefore,
securing adequate freshwater for all life and human activities is a premier and precondition aspect to achieve sustainable development.
Humans rely on nite supplies of freshwater to stay alive. Unfortunately, although water may cover more than 70% of the Earth's surface, 98%
of that is saline water and out of the 2% of fresh water, 90% of it is frozen
in glaciers [1]. Many countries face water scarcity as a fundamental
challenge to their economic and social development. Water use has
been growing at more than twice the rate of population increase in
the last century [2,3]. It is also predicted that by 2030, over one third
of the world population, concentrated in developing countries, will be
living in river basins that will have to cope with signicant water stress.
This including many of the countries and regions that drive global economic growth and two-thirds of the world population could be under
stress conditions. Based on the alarming projections by United Nation,
nearly 7 billion people in 60 countries will suffer from water scarcity
by 2050. Even according to conservative projections, just under 2 billion
people in 48 countries will struggle against water scarcity in 2050 [4].
With world population expected to pass 9 billion by mid-century, solutions to water scarcity problems are a great challenge to be tackled.
Achieving good accessibility to freshwater in sufcient amounts and
of suitable quality is the key focus and hence the heart objectives of
many international policies. United National Millennium Development
Goals (MDGs) aims to halve the proportion of people without sustainable access to safe drinking water by 2015, which means improving
water supplies for 1.5 billion people according to the World Water Assessment Programme [4]. The world is increasingly turning its attention
to the issue of water scarcity. The need for fresh water is therefore at the
top of the international agenda of this critical problem [5].
Intensive efforts are underway throughout the world to avert this
looming crisis. The recent advancement made in water treatment
science and technology research has alleviated the water scarcity stress
by addressing the problems with high quality and sustainable water
supply. Different approaches have been reached to overcome the
shortage water problems, including seawater and brackish water desalination and recovering the treated industrial waste water. Among the
conventionally used methods, seawater and brackish water desalination through various desalting technologies seems to be the most
straightforward undertaken approaches that hold great promise to
effectively increase water supply by generating more freshwater from
sea and inland saline aquifers for the world usage. Since the sources of
seawater and brackish water account for almost 98% of all water on
the earth, capturing a tiny fraction is expected to impart a huge impact
on the water scarcity issues [6]. Research and development into
improving desalination technologies are now actively ongoing, especially in Saudi Arabia, Israel and Japan, to study the feasibility of large
scale desalination plants for municipal water supplies.
Membrane engineering has been widely accepted as a possible route
to offer sustainable fresh water production in a more advanced and
environmentally acceptable process due to the recent advancement
made in material chemistry that is coupled with the needs for processes
with low energy consumption. Membrane-based water purications
are well recognized as a versatile technology for a wide spectrum of
water and wastewater treatment processes. Membrane processes
have the potential to replace conventional energy-intensive separation
technologies such as distillation and evaporation which commonly suffer from disadvantages such as high cost and requirement for the use of
chemicals that need special handling. Currently, the major desalination
technologies are based on membrane separation via reverse osmosis
(RO). Remarkably, seawater reverse osmosis (SWRO) technology has
surpassed distillation in this decade and is awaited to be the technology
with signicant advances for current and future implementation [7].
Also, brackish water reverse osmosis (BWRO) is increasingly being
considered as a promising source of drinking water in the near future.

Recent survey done by the International Desalination Association

showed that about 19% of the desalination plants in the world are
installed for brackish water desalination [8]. Some of the major issues
to be addressed in desalination concern the high energy cost, the pretreatment optimization as well as the environmental impact imparted
by large scale desalination plants. For a membrane-based desalination
system, enhancing water ux without sacricing the salt rejection as
well as the membrane fouling resistance have been identied as the
key economic drivers in which these factors translate directly to the
energy intensity and capital expenditures of the system [9].
RO technology has become a critical technology to assure the supply
of freshwater due to its inherently simple design and operation and to
enable it to serve as one of the most energy efcient techniques for
seawater desalination purposes [10,11]. In fact, it has been reported
that membrane-based desalination accounts for about 44% of the
installed capacity of water desalination in the world [12]. Very recently,
forward osmosis (FO) and membrane distillation (MD) as well as
non-membrane electrochemical technologies such as capacitive deionization (CDI) have been explored for the potentials as alternative desalination technologies to offer low energy consumption while achieving
high water recovery. These technologies are emerging to provide wider
options, but have yet to nd practical and commercialized applications.
Research efforts are underway to seek for breakthrough of these technologies to compete with and surpass the performance of conventional
RO and thermal desalination.
The desalination science and technology is undergoing an awesome
revolution in which a new paradigm of research involving the use of
nanotechnology is evolving rapidly. Future technology has focused on
the application of nanotechnology in which wide attention has been
spurred on the development of nanomaterials in advancing the existing
technologies of various elds. Carbon nanotubes (CNTs) are increasingly investigated and they have been proposed as a promising option for
enhancing the efciency and capability of currently available desalination system in order to meet the municipal and industrial water supply
demands. Additional research on novel applications of CNTs in desalination has offered tremendous opportunities and possibilities for
further improvement in this technology. Introductions and applications
of CNTs in the innovative forms emerge as an attractive and viable
approach for the next-generation desalination technologies.
CNTs have particularly attracted signicant growing attention due to
their capability to display superior durability and separation characteristics. The introduction of CNTs constitutes a signicant potential breakthrough for the desalination technology. Previous research studies on
the transport properties of CNTs have commonly found that the
extremely smooth hollowed structure of the nanotubes could facilitate
rapid transport of liquid and gas molecules in the channels, hence can
favorably offer high ux membrane separation performance. Diameter
of the CNTs is the critical dimension to implement physical size exclusion and capillary behavior relevant to the environment systems.
Extraordinarily, the small and precise diameter size of CNTs is also
proved to reject most ions due to the energy barrier existing at the
channel entries hence only water molecules are allowed to permit
through the nanotube hollows [13]. The ndings from some of the
simulation studies have interestingly showed that water can enter
narrow hydrophobic interior channels of CNTs, which have been conrmed experimentally and have opened the door to the incorporation
of CNTs into membrane to form smooth pores for the desalination applications [14]. Additionally, the structure of CNTs could permit the
targeted specic modication of the pore entrance to facilitate selective
transport, without altering or destroying the properties of the inner
nanotube surface [15]. Expectedly, the fast and selective uid transport
observed in CNTs has very soon sparked many ongoing scientic discussion and research to make use of this unique feature. The studies on
water transport through CNT channels are of great importance for
using these nanomaterials for both seawater and brackish water desalination. It has also been documented that the application CNTs can be

P.S. Goh et al. / Desalination 308 (2013) 214

favorably imparted with anti-microbial properties thus alleviates the

commonly faced fouling issues. By virtue of this, CNTs appear to be a
suitable candidate that holds very bright prospective to be readily
adaptable for commercial use to battle the weakness of the currently
available desalination technologies.
Research has shown that a doubling of membrane ux with constant
rejection through the incorporation of nanoparticles could be used in
several operating modes such as SWRO and BWRO to decrease energy
cost or increase system output. This has in turn been translated into
almost 13% reduction in the cost of the desalination plant as this form
of nanocomposite membrane shows promise as having low fouling
surfaces [9]. Research on the transport of water through CNTs demonstrated that water ux through the hollowed structure is over three
fold of magnitudes due to the atomically smooth and hydrophobic
wall that allows considerable slip of water through the hollow channels
[16,17]. Further investigation demonstrated that the ux of CNT incorporated membranes has exceeded that of the commercial NF membrane as much as four times [18]. Since there is a pressing need to
improve the present desalination technologies, focus and attentions
are urgently required to evaluate the practical performance and impact
of CNTs in the desalination application.
Despite the current state-of-the-art desalination technology that
is exploiting the advantages of CNTs, several challenges and hurdles
encountered in the development of this newly emerging technology
are still remaining as the major concerns of the worldwide desalination
industries. Substantial uncertainty also remains about the technology's
environment impact. Therefore, efforts to expand and fully harvest the
advantages of CNTs may face great challenge in the near term. With
the major focus placed on the utilization of CNTs, this paper rst
outlines the current desalination technique in use and followed by a
comprehensive review on the current and future trends in the CNT
incorporated desalination technology. Within this context, the recent
research on the transport properties and chemical functionalities
that have great relevance to the feasibility and applicability of CNTs
for water desalination is summarized. Through the evaluation of the
performance of CNT-based desalination, the existing hurdles and upcoming challenges related to the application of CNTs in desalination
technology are highlighted. This review is expected to provide indepth insight and understanding to the future development of next
generation of CNT-incorporated desalination technology that is anticipated to impose remarkable global impacts in this eld. With the
constant improvement achieved in all aspects, it is anticipated that it
is just the matter of time for this novel nanostructured materials to
likely play an essential role in shaping the future trends in membrane
material research.

2. Emerging nanotechnology for water desalination

The rapid growth in nanotechnology has advocated blooming interest in the environmental applications of nanomaterials particularly to
revolutionize the century-old conventional water treatment processes
[10]. The emerging nanotechnology displays excellent vitality and
catches increasing attention from both academic and technology points
of view. The availability of different types of nanostructured materials
with the improved knowledge and skills on the production of various
forms of structurally engineered novel materials has opened new
doors in the development of functional membranes. Many researchers
and engineers claimed that nanotechnologies offer more affordable,
effective, efcient and durable ways of achieving molecular manipulation [19]. It is anticipated that the use of nanoparticles for water desalination will allow the production of more competitive materials that
requires less labor, capital, land and energy. [20]. More desirably,
nanoparticles can be easily designed to produce tailor-made particles
for specic applications. Currently, a wide range of water desalination
technologies based on the incorporation of nanomaterials are available

on the market, with others either close to market launch or in the

process of being developed.
The unique properties of nanoscale particles make them particularly well suited for treating water. The emergence of nanotechnology
in membrane based desalination offers an attractive alternative to the
existing polymeric materials. Nano-enabled technologies include a
variety of different types of membranes based on zeolites, carbon
nanotubes, graphene, nanoporous ceramics, and other nano-metal
oxide particles such as TiO2 [10]. The effects of nanomaterial particles
when integrated into a desalination membrane can be varied. The presence of these nanoparticles may give rise to the increase in skin layer
thickness and surface porosity of the skin, suppressed macrovoid formation, higher permeability and salt rejection. Nevertheless, the main
purpose is most probably to serve combined effects of fouling resistance
and ux enhancement [21]. Researchers have attempted to modify the
surface of membrane for the synergistic performance in water desalination. For instance, the fast transport properties of aligned CNT channels
have been utilized to improve the water ux of polymeric membrane;
the shape selectivity and specic sorption characteristics of zeolite can
be combined with easy processability of polymer to provide desired
salt rejection features and also, the catalytic properties of titanium
oxide particles are expected to mitigate membrane fouling with their
built-in oxidative functionality [22].
Nanotechnology is expected to further improve membrane technology and also drive down the high costs of desalination. In this so
called next generation membrane, high permeate production is
achieved by allowing the desalination plant to operate at increased
ux and recovery. This effort is made through the engineered assembling of nanomaterials into porous membranes or via the incorporation
into polymeric and inorganic membranes to bring about tremendous
improvement in water ux and alteration of surface properties potentially related to fouling while maintaining or slightly increasing in the
salt rejection [21,23]. With these improvements, less energy is needed
to pump water through the membranes. Also, through the proper incorporation of nanomaterials in membranes inactivation of irreversibly
adhered microorganism can be achieved, making it possible to minimize the fouling [10]. This form of membrane is found to foul more
slowly than the conventionally used membrane as it exhibits stronger
repellence towards the particles that might ordinarily be adsorbed
on the surface. The result is a water purication process that is just
as effective as current methods but more energy efcient and potentially much less expensive. Initial tests suggest that the new membranes have up to twice the productivity, or consume 50% less energy,
reducing the total expense of desalinated water by as much as 25%
[22,24,25].
Since the last few decades, the improvement in nanocomposite
membrane performance using zeolite as the dispersed phase has
resulted in the commercial alternative over the polymeric and inorganic
membranes. Zeolite nanoparticles have been potentially incorporated
into polymer matrix to form thin lm nanocomposite RO membrane
to create preferential ow path for water molecule, leading to enhanced
transport and productivity of the water molecules [2628]. The use of
zeolite in the development of thin lm nanocomposite membranes for
RO has been rst reported by Hoek and co-workers [29]. Similarly,
Jeong et al. [26] prepared the thin lm RO nanocomposite membrane
by interfacial in-situ polymerization on porous polysulfone support in
which NaA zeolite nanoparticles were incorporated into the thin polyamide lm. The introduction of zeolite nanoparticles in the conventional polyamide RO thin lm has performed enhanced ux to more than
double of the conventional membrane and salt rejection of 99.7%,
which is attributed to the smoother and more hydrophilic negatively
charged surface. Silica nanoparticles of various size have also been
incorporated into polyamide polymer matrix for RO desalination [30].
The presence of nanoparticle silica was found to remarkably modify
the polyamide network structure, and subsequently pore structure
and transport properties, whereby with only 12 wt.% of silica, the

P.S. Goh et al. / Desalination 308 (2013) 214

membrane with signicantly enhanced ux and salt rejection can be

fabricated.
In conventional adsorption-based desalination, CNT sheets have
been used as an effective adsorbent for seawater desalination due to
their extraordinarily high adsorption capacity [31]. In fact, it has
been veried that CNT adsorption technology has the potential to
support point-of-use water treatment approach for effective removal
of pathogens, natural organic matter and cyanobacterial toxins from
the water system [32]. Particularly, oxidation of CNTs prior to the
fabrication of CNT sheets offers a great number of surface functionalized
groups with hydrophilic surface structure. The increased amount of
surface total acidity is the main factor that gives rise to the improved
ion adsorption. The use of CNTs in membrane-based desalination is
shown to be promising as a candidate for water desalination. One of
the most outstanding properties of CNTs that make them attractive for
water transport and desalination is the size and uniformity of the
tubes, as well as the atomic scale smoothness and chemical inertness
of the graphitic wall that could favorably allow them to achieve desired
water ux and salt rejections [33]. It has been indicated that nanotube
membranes may prove to be extremely effective for water ltration
and may produce a viable water desalination process that would
require substantially less energy than reverse osmosis in the near future
[34]. Graphene, a new class of carbon nanomaterials with novel properties similar to CNTs, has also found its potential application in simultaneous removal of high concentration of arsenic inorganic species and
sodium ions using supercapacitor based water lter [35]. Cost effective
production of graphene sheets and more outstanding performance
compared to other conventional adsorbents such as activated carbon
provide a feasible platform for the commercial development of this
material.
It is worth saying that, in this relative short period of its development, these nanocomposite membranes have shown the performance
that transcends that of commercial RO membrane materials based on
the standardized polymer chemistry that have been used in the last
few decades [9]. This technology is now in the process of being commercialized with trials on a specially designed full scale manufacturing
line underway. Despite of the stimulating ndings of nanotechnology in
desalination, there remain few drawbacks in regards with this technique which includes the insufcient data on the long-term operation,
chemical stability and scale-up information. These issues are of great
urgency and need to be looked into and overcome before any successful
commercialization of the desalination technology that is based on the
manipulation of nanotechnology [10].
3. Carbon nanotubes as potential materials for water desalination
CNTs can be conceptually described as a one dimensional analog
of zero-dimensional fullerene with a micrometer-scale graphene
sheet being rolled into a cylinder of nanoscale diameter. Depending
on their synthesis methods, CNTs can be produced as singlewalled
CNTs (SWCNTs) or multiwalled CNTs (MWCNTs). The synthesis and
applications have been extensively reviewed and published [3640].
Generally, the increased attentions to CNTs from wide disciplines
arise from the fact that CNTs can be potentially applied in many elds
of science and engineering with the current material science advancements. A diverse array of innovative methods have been developed
to assemble CNTs into devices for a broad range of applications. As
mentioned earlier, the recent development of CNTs has asserted the
unprecedented rapid growth in the eld of desalination. In fact, the
introduction of CNTs in water industry is not a new topic. For almost a
decade, CNTs have been actively researched for their capability to
serve as adsorbent media to remove a wide range of chemical and biological contaminants. The CNT adsorption technology has been critically
addressed and extensively reviewed previously [41,42]. The outstanding outcomes achieved in the adsorption capability of CNTs are mainly
attributed to its structural and functional properties, as well as the

microbial cytotoxicity that has a partial inuence in concentration of

biological contaminants. Only very recently, the need to further enhance the performance of desalination technologies by using alternative methods has pushed this nanostructured material to the forefront
of applications due to their outstanding water transport properties.
High concentration of ions in seawater and brackish water frequently causes high tendency of membrane scaling through the precipitation
of sparingly soluble salts. Moreover, with the continual emergence of
micro contaminants that most probably causes membrane biofouling,
desalination approaches are designed to achieve multiple treatment
objective in a single reactor [12,43]. In order to mitigate the fouling
issues, strategies like pH adjustment, antiscalant addition and chemical
cleaning have been widely used [4446]. It is worth mentioning that,
the application of CNTs in desalination also endows some other signicant advantages instead of it exceptional transport characteristics. Due
to the inherent cytotoxic nature that can prohibit the bacteria growth,
CNTs possess outstanding biofouling resistance that is highly desired
in various forms of desalination methods [47]. The detailed and comprehensive description on the role of CNTcomposite in preventing
biofouling has been presented by Upadhyayula and Gadhamshetty [48].
3.1. Water and ion transport in carbon nanotubes
Due to their high hydrophobicity and structural simplicity, CNTs
have been considered as a model system to study the water and ion
transport as well as the waterion interaction based n their nanoconned inner cores [49,50]. In fact, the structure of CNTs has been
proposed to closely mimic some biological pores based on their similarity in size and hydrophobic nature [51]. The water transport through
CNT channels represents a unique nanouidic system and it has
exhibited similarity between their uid transport properties and those
of water transport channels in biological membrane [16,52]. Although
the rapid water transport has yet to be fully understood, it has been
proposed that the Weak interactions of water molecules with the hydrophobic walls combine with the smooth nature of the walls to enable
nearly frictionless transport of water to facilitate the high ux water
transport [52]. Arguably, it has also been suggested that shielding effect
established through the formation of a layer of liquid water molecules
along the CNT channels is the primary reason for the frictionless
water ow [53]. The high uid ux observed is contributed by atomicscale smoothness of the CNT walls and the molecular ordering phenomena inside the nanopores [54]. In order to fully utilize CNTs as a hollow
structured material for rapid water transport, a greater understanding
of the uid ow in the cylindrical channel is therefore highly desired.
Computer modeling approaches have been used to predict and evaluate
the performance of an intact CNTs on the ux and salt rejection properties. This information is critically valuable for the widespread application of CNTs in which the theoretical outcomes could provide a
precise engineering approach for using CNTs as a transporting medium
for water molecules, particularly in desalination applications [55]. To
date, a huge number of theoretical CNTs transportation characteristics
have been modeled and documented [16,5659].
The theoretical studies which use various combinations of molecular dynamic simulations and single-le transport model have been
established to gain understanding on the transport mechanisms of
water molecules when passing through the CNT channels. Molecular
dynamic modeling has demonstrated that water ux through CNTs
can be several magnitudes greater than that of conventional pores.
One of the remarkable ndings on the lling of CNTs with water molecules has been reported by Hummer et al. [16]. They have revealed
that the nanoscale connement, in this case the connement in nanotube channels, could lead to the narrowing of the interaction energy
distribution, which in turns lowering the chemical potential and free
energy. The subsequent examination by Kolesnikov and co-workers
[60] discovered that the connement of water molecules has induced
stronger attraction between the water molecules than the interactions

P.S. Goh et al. / Desalination 308 (2013) 214

with the CNT walls. These ndings provided mechanistic insights into
the extremely rapid water transport by providing explanations for the
inuences of the CNT structural change on the ux for the transport of
liquid and gases through the CNTs [15].
While CNTs exhibiting rapid water ow through its inner cavities,
the electrostatic charge distribution on the CNTs may change the CNT
intake effectiveness and induce different effects on water and ion
separation. The feasibility of ion transport and adsorption using electrostatically charged CNTs has been studied by Banerjee et al. [61] who
observed that the spatially alternating charge patterns placed on CNTs
have favored water intake but entirely inhibit ion intake into the
nanochannels. The results have in turn pointed out that, by manipulating the applied charge pattern, the CNTs can be favorably used as water
or ion encapsulation devices. The theoretical studies on the transport of
water and ions through CNT channels conducted by Corry and coworkers [13,62] revealed that with a certain range of CNT hollow diameter, only water molecules were permitted to pass through rapidly,
whereas the passage of ions was hindered. The selectivity features
that act towards different ion types with different nanotube diameters
have demonstrated the potential of CNTs to serve as membrane to
improve desalination technologies. Furthermore, the extremely high
water ux obtained from the simulation has given a new insight to reduce the desalination cost via fabrication of CNT-based RO membrane.
The curvature of the CNT graphitic surface has also been identied
as a determining factor for the friction coefcient between the water
molecules and the CNT walls. Falk et al. [63] have interestingly found
out that the curvature regulates the interaction energy between
water molecules and CNT wall such that the friction is higher for
water molecules interacting with the outer surface of CNTs and the
magnitude of friction decreases with decreasing CNT diameter. This
observation has been further veried by Melillo et al. [64] who have
shown that the interaction strength between water molecules and
the wall materials of CNTs has a signicant impact on the ability of
water molecules to enter and reside in the nanotubes. More recently,
molecular dynamic simulations have also been adopted by Zuo et al.
to investigate the single-le water transport through CNTs under a biased electrostatic potential [65]. They found that water ow was easily driven by external elds but concerted transport has been
constantly observed through the nanotubes. This phenomenon can
be ascribed to the polar and van der Waals interactions of the
transported water molecules with other water molecules both inside
and outside the CNT.
3.2. Modication of carbon nanotubes for salt rejection

structural variety and render them a highly customizable material.

Unfortunately, due to the inconsistency of synthesis and modications,
variation between samples is a challenge for further research on the implication and commercial applications of CNTs.
Resolving these characteristics has become as imperative for
multidisciplinary applications of CNTs from both technical and environment perspectives. Different strategies have been considered for the
prevention and control of this problematic phenomenon. Chemical
modication and functionalization are commonly required for the application of liquid ux in CNTs to attain selective and controlled transport. Various purication and functionalization schemes have been
extensively developed and provided in several review articles [6769].
In general, the different approaches to functionalization may yield in
three main forms of CNT membrane as depicted in Fig. 1: i) plasma
oxidized membrane with a few carboxylic acids at the CNT tips; ii) tip
functionalized CNT membrane through chemical modication and
iii) core-functionalized membranes via chemical grafting along the
CNT axis [70]. Remarkably, these primary results have suggested that
there lies great potential for further improvement through more feasible structural modication and optimization of this material.
When the pore diameter for channels is less than 1 nm, it would
lead to a large free-energy barrier resulted from the stripping off of
the hydration shells of ion and water molecules. Therefore, surface
modication is required to alter the surface properties and hence decrease the energy barrier [6]. In addition to that, in order to allow desalination of the ions with hydrated radius ~0.358 nm and to attain high
salt rejection, the diameter distribution of the nanotube must be precisely narrowed; hence more complicated and precisely controlled
synthesis conditions are required which remains as a substantial
challenge [41]. Technological solutions to defeat the abovementioned
problems include the functionalization of the tip of the pores to increase
selectivity and potentially increase the hydrophilicity at the surface.
Oxidation and other forms of chemical modications of CNT with
hydrophilic functional groups may increase the binding energy between water and the nanotubes, hence facilitate water ux [71]. Steric
channel gating of large CNT pores offers an interesting option to rene
the selective capacity of CNTs, as well as reduce the selectivity dependence on small variation in the CNT diameter. It has also been suggested
that electrostatic and van der Waals interaction may also hold important role to achieve the desired selectivity [72]. Practically, the ionic
transport through nanotube membrane can only be achieved if the
nanotube is precisely gated with selective and controlled chemical
interaction to enhance the range and functionality of the CNTs. Thereby,
few attempts have been carried out to actively control pore surfaces in

The conceptual transport performance of CNTs was often established by considering the water transport in an individually isolated
intact CNTs. However, the production of ideal CNTs remains a challenge and yet to be fully accomplished. In reality, the manufacture
of such membranes is difcult and prone to have defect formation
as well as costly. These hurdles have shed some doubt to the feasibility of CNTs for its practical applications. In particular, aggregation of
CNTs has allowed profound increase in the ux but inevitably led to
increased salt passage that eventually declines the salt rejection properties of the membrane. Commonly, the commercially available
SWCNTs and MWCNTs suffer from defects, metal catalyst contaminations and physical heterogeneities [41]. When CNTs are employed in
other applications, one of the most important measures to be taken
in order to advance CNTs in the eld of desalination is the necessities
to get rid of the impurities in the pristine nanotubes and to overcome
the difculties of dispersing and processing due to their nature that
tends to form agglomerates rather than as an individual tube. Moreover,
even though CNTs have been generally depicted as open-ended tubes,
their ends are usually capped by higher curvature of fullerene-type
hemisphere [66]. The CNT tips with greater reactivity can be further
exploited to selectively functionalize the ends of CNTs to result in

Fig. 1. Illustration of the position of the functional groups in the CNT-tips and CNT-core
[70].

P.S. Goh et al. / Desalination 308 (2013) 214

order to alter occupancies and ux of ionic species for separation

purposes.
Using molecular dynamic simulation, Joseph et al. [73] showed
that symmetrical functionalized nanotubes with charged \COO
and NH3+ attached at the end and in the tubes could conduct ions in
the presence of an electric eld as well as achieve the cationic and anionic selectivity. This nding is important for the particular interest to
functionalize CNTs with small diameter in which the presence of
charged functional groups at the CNT tip may enable the control of
ionic ow and the exclusion of very small ions. This is at particular
interest for water desalination applications. Goldsmith and Martens
[74] have also provided some evidence for the enhancement of ion
rejection, in which they attributed this underlying mechanism to both
direct electrostatic interactions between the surface charges and solution ions as well as the indirect effect of the water structuring induced
by different charge pattern. It is worth-noting that similar prediction
has been reported in the earlier molecular simulation carried out by
Park et al. [75] in which Y-junction nanotube was constructed by
connecting two smaller carbon nanotube branches of sizes (5, 5) and
(6, 6) to a larger (8, 8) carbon nanotube. They observed that as the electrolyte moves through the (8, 8) carbon nanotube the K +and the Cl
ions can be selectively transported through the negatively charged
(5, 5) and the positively charged (6, 6) carbon nanotube, respectively.
The (5, 5) CNTs with diameter of 0.34 nm conducted K + ions while excluding Cl, meanwhile (6, 6) CNTs with positively charges decorated
on its external wall have favored the passage of Cl. However, the prediction is yet to be veried as to date the CNT membrane with such
small diameter has not been successfully fabricated.
Very recently, Corry [14] employed molecular dynamic simulation
to examine water and ion transport through functionalized CNTs
instead of an idealized CNT model, in order to examine the impact of altered surface chemistry on the ux and salt rejection performance of
wide pore CNTs in water desalination. The snapshots in Fig. 2 illustrate
the functionalization of different polar charged functional groups at the
CNT pore entrances. Since the inclusion of negatively charged groups
effectively prevented Cl and positively charged groups could repel
the Na+, almost complete rejection of both types of ions has been
achieved by the CNTs functionalized with COO and NH3+. On the
other hand, a noticeable reduction in the water ux has been observed
in the functionalized CNTs compared to that of idealized CNT model due
to the removal of the smooth neutral internal channels upon the
functionalization. This unfavorable phenomenon suggests that steric
blockage may take place either by the functional groups or by the ions
that were attracted and saturated at the nanotube opening. Another
plausible explanation for the depletion of water ux is the introduction
of signicant direct interactions between the water molecules and the
functional groups which consequently prompted the temporarily
pause of water molecules around the functionalized regions. Similar
anomalous decline of the water transport has also been previously
reported by Joseph et al. [76] where they claimed that lower water
ux has arisen from the mechanically rough surface of the CNTs upon
the functionalization. The surface roughness increased the turbulence
of the water in the nanotube channel and destabilized the structure of
the water near the interface with the CNTs that are responsible for
rapid water transport. Despite the slight ux deterioration compared
to unfunctionalized CNTs, the functionalized CNTs exhibited ux that
is greater than the existing commercial polymeric RO membrane,
which allows the possible practical application of the functionalized
CNTs in desalination technology.
Fornasiero et al. [18] performed functionalization of carboxyl groups
at the pore entrance of a large diameter CNT array to achieve high salt
rejection capability through electrostatic repulsion. The presence of
the functional groups exerts electrostatic repulsion to allow exclusion
of salt ions. Salt rejection of nearly 100% has been achieved, particularly
for the salt solution with greater anion valence charge such as
K3Fe(CN)6. However, it has also been observed that salt rejection was

Fig. 2. The snapshots from molecular dynamic simulation illustrate the functionalization
of the CNT pore entrances with A) COO, B) NH3+, C) combination of COO and NH3+
and D) OH [14].

poor for high salt concentration that corresponds to a smaller electrostatic Debye screening length. Fig. 3 illustrates the schematic of CNT
membrane and the salt rejection prole as function of salt rejection
and Debye length. Yu et al. [49] prepared dense vertically aligned CNT
membranes by capillary force driven shrinkage of CNT array grown by
chemical vapor deposition. They reported that the ion diffusion in CNT
membrane exhibited a gated behavior due to the changes of water
wettability on hydrophobic surface of the CNTs. It is revealed that the
ion transport increased to a rate similar to bulk diffusion in water
with the increasing temperature or when the membranes were
subjected to ultrasound. At higher temperature, more water in the
CNT pores increased the likelihood of forming continuous water channels in dense CNT-membranes for ion diffusion. The ndings have
implied that that temperature needs to be carefully controlled or else
ion transport will be rapid.
4. Performance evaluation of carbon nanotube material for
water desalination
The advances made for CNT applications offer new avenues to
address the challenges faced by current desalination technologies. The
remarkable progress in the molecular manipulation of CNTs opens
the possibility for this material to directly participate in establishing
innovative water desalination technology. To evaluate the performance
and hence viability of CNTs for water desalination, detailed investigations on the ux and salt rejection are essential. Additional requirements in the aspects of mechanical strength and stability to resist
membrane deterioration should also be taken into consideration. In

P.S. Goh et al. / Desalination 308 (2013) 214

Fig. 3. A) CNT with \COOH functional groups at the pore entrance, salt rejection prole as a function of B) feed water concentration and C) the Debye length [18].

this section, the development and application of CNT materials in desalination technology are highlighted with focus on their possibility to be
engineered into potential materials to heighten the performance and
efciency of the named desalination technologies.
4.1. Carbon nanotube membranes
Dumee et al. [77] produced self supporting CNT Bucky-Paper (BP)
membrane through vacuum ltration technique. The paper-like structure of CNTs, which only held together by the van der Waals force without the aid of any binding agents, was applied for desalination in a direct
contact MD system to serve as the alternative that is able to overcome
some inherent limitations of currently available MD membranes.
These BP membranes exhibited promising properties that are favorable
for MD desalination, such as high hydrophobicity, high porosity, high
specic surface area and relatively low thermal conductivity, which
have suggested the potential use of this material to surpass the performance of conventionally used PTFE membranes that have been typically
used as benchmark of MD process. The research group has observed up
to 99% salt rejection with highest ux rate of 12 kg/m 2 h at a water
vapor partial pressure difference of 22.7 kPa. Despite the bright prospective of this BP membrane to provide better option to MD desalination, this material endured signicant decline of water ux with
prolonged operation time due to temperature polarization that limited
water permeability by creating a stagnant boundary layer on the surface
pores. Delamination of the membrane could also likely take place due to
the formation of micro-cracks (Fig. 4) at the CNT membrane that initiated water to be drawn in via capillary forces. To address these issues, two
viable approaches that involve the chemical modication of CNTs have
been conducted by the same research groups: i) UV/ozone treatment to
create hydroxyl and carboxylate active sites, which were later substituted with alkoxysilane based groups [78] and ii) coating of a thin layer of
poly(tetrauoroethylene) (PTFE) [79]. Since it has been previously
reported that high hydrophobicity is of great importance to achieve
high ux in MD [80,81], thereby the enhanced hydrophobicity upon
the chemical functionalization as well as PTFE coating has consequently
led to improvement in membrane ux. This is due to the higher hydrophobicity of material that could increase the water meniscus surface
hence offering more exchange surface available for water evaporation.
The improved lifespan of the membrane can also be attributed to the

increase stability of the membrane upon the modication. The valuable

features of the modied CNT BP membranes promise their use in the
current development of MD desalination process.
To establish a synthesis method for CNT membranes with more simplicity and viability, Toghy et al. [82] produced CNT membrane directly
on macroporous surface of -alumina support followed by acid oxidation treatment. They observed fast water permeation through CNT
inner cavities and sodium ion retention, in which they have subsequently suggested that the chemical interactions between the sodium
ions and the acidic functional groups can facilitate free water permeation through CNT channels. During surface modication, a large
number of chemical adsorption sites were introduced to the surface
of CNT-membranes. With the elevating temperature, the ion uptake
capacity of CNTs increased, hence the number of free accumulated
ions around the membrane surface decreased to allow easy water permeation through the CNT inner cavities. The similar effect could also
be observed by increasing the ion feed concentration. As a result, the
permeate ux can be enhanced without causing serious concentration
polarization effect on the performance of the CNT membranes.

Fig. 4. SEM cross section of CNT-bulky paper shows the presence of micro-cracks and
delamination of CNT layers [77].

P.S. Goh et al. / Desalination 308 (2013) 214

Fig. 5. Molecular dynamic simulation is conducted using CNT membrane formed by

hexagonally packing 12 CNTs in a periodic cell [13].

Performance evaluation through Taguchi method has showed that by

increasing the feed concentration, temperature and ow rate, while
decreasing the operating pressure are some of the parameters that
could optimize the desalination performance of the CNT membranes.
The good consistency of the predicted and experimental results has
implied the potential use of this membrane to reduce energy cost of
desalination process compared to conventional RO membranes due to
the low pressure operation and robustness of the membrane to resist
various compounds and harsh environments.
The transport of water and ions in CNTs with different diameters
ranging from 6 to 11 when used in RO system has been quantied
by Corry using molecular dynamic simulations in which the CNT
membrane is formed by hexagonally packing 12 CNTs in a periodic
cell as shown in Fig. 5 [13]. In order to perform an efcient desalination,
the diameter of CNTs must be precisely controlled to reject the passage
of ions through the nanotube channels in which the CNTs with diameter
greater than (8,8) pore would not likely be a sizeable barrier for the ion
permeation. The results suggested that membranes incorporated with
carbon nanotubes can be principally used to achieve high degree of desalination using RO system at the ux that is much higher than that of
existing membranes through the careful tailoring of the CNT core size.

Past

1997

1997

gold CNT for

macromolecule
separation
wide pores CNT
for increased flux

2004

2005

Similarly, the application of CNT membrane as possible candidate for

FO desalination has been investigated by Jia et al. [83] by means of the
molecular simulation. The feasibility of the CNT membrane for water
desalination in FO process was proven where the transport of water
through the CNTs was extraordinarily fast, when compared with that
of the transmembrane protein aquaporin-1 serving as a biological
water channel. The rough estimation showed that CNT membrane can
achieve far higher water ux than the existing commercial FO membranes. The CNT membrane is also found to exhibit salt rejection of
100% with the optimized diameter size of CNT (8,8). The outcomes of
the study implied that the FO membrane comprising the specically
sized CNTs could demonstrate anti-trade-off property.
The several previous studies, which mostly based on computational
prediction, have somehow given a clear indication on the potential of
CNT membrane to serve as an efcient membrane that can perform
high salt rejection while maintaining large throughput in water desalination. In reality, the application of CNT membranes under large hydrostatic pressure normally requires the CNTs to be packed within a solid
nonporous material to prevent them from separating apart [13].
Hence, lling the inter-tube gaps of CNT array and removal of the excessive lling layer are the crucial steps that need to be taken into consideration during the CNT membrane synthesis [82]. The preparation of
free standing and silicon-chip supported vertically aligned CNTs by
Hind et al. and Holt et al. [84], in their pioneering work mentioned in
the earlier section, was completed using complex synthesis method.
The ultimate goal to produce individual isolated CNTs as well as densely
packed vertically aligned arrays still remains deceptive as it requires
considerable process development and optimization efforts [15]. Therefore, future research and investigations are necessary to verify the feasibility and practicality of this form of free standing or vertically aligned
CNT membranes in a large scale industrial application for desalination.
Fig. 6 illustrates the evolution of CNT-membranes from macromolecule
chemical separation to tunable membranes for nanoltration. The development of high ux, selective and antifouling membrane is expected
as the future highlights for desalination applications [41].

4.2. Carbon nanotubes/polymer mixed matrix membrane

One of the promising approaches of applying CNTs in desalination
technology is through the incorporation of this material within a continuous polymer phase to form a so-called mixed matrix membrane
(MMM) to simultaneously perform enhanced separation performance,
mechanical stability as well as advanced functionality [85]. MMMs consist of inorganic llers incorporated into a polymer matrix and have the
potential to extend or even surpass the separation benets exhibited

2006

aligned and functionalized

MWCNT membrane for ions
separation

2007

2012

Future

aligned and functionalized

MWCNT membrane for tailored
polarized and voltage- selectivity and antifouling
gated CNT for
nanofluidic applications

Fig. 6. Evolution of CNT-membranes from macromolecule chemical separation to antifouling and desalination applications [41].

10

P.S. Goh et al. / Desalination 308 (2013) 214

Fig. 7. Mechanisms of MD in the presence of CNTs [91].

by the polymeric membrane platform. The concept of MMMs was rst

introduced in 1980s to overcome the limitation of polymeric membrane
in gas separation. Molecular sieve such as zeolite and CMS has been
conventionally packed in the polymer phase to form a dense region of
mixed matrix layer. These nanoporous materials possess the shape
and size of selective nature and hence allow molecular sieving discrimination by permitting smaller sized penetrates to diffuse at higher rate
than that of larger sized. The introduction of MMMs as RO TFC membranes was only initiated in the early 2000s [86]. While polymeric
membranes are likely to dominate membrane-based desalination technology, further improvement on the membrane diffusion performance
is incremental and value added. Previously, thin lm nanocomposite
incorporated with inorganic llers such as zeolite, silica and titanium
oxide nanoparticles of various sizes has been developed to achieve
promising performance with respect to ux and rejection [8789].
Novel membrane that consists of polymeric materials incorporated
with CNTs as the inorganic dispersing phase is expected to signicantly
reduce the energy and cost of desalination [6]. Fundamentally,
MMMs are polymer composites that involve phase separated membrane separation system. In this structurally engineered hybrid membrane, inorganic llers act to create preferential permeation pathways
for selective permeability. The superior permeability and selectivity of
inorganic llers with the processability of polymeric materials are combined to achieve synergistically improved separation performance.
CNTs have been identied as a suitable ller to be embedded into a
polymer matrix to manufacture CNT/polymer membranes granted with
rapid water transport. In fact, the impressive combination offers new
degree of freedom in designing the desired membrane by manipulating
the composition and interactions of the host polymer matrix and

dispersed llers, which eventually inuences the characteristics and

performance of the resultant MMMs. This is expected to create unlimited possibilities to impart a wide array of separation performance and
novel functionality. By considering the small diameter of CNTs that
allows smooth and frictionless water transport, the incorporation of
CNTs in a polymeric membrane may offer a better alternative in tuning
the membrane structure, hence contributing to the improved separation
performance. It has been suggested that, the incorporation of CNTs has
disrupted the polymer packing in the membrane and created nanoscale
cavities in the coating layer to enhance the water ow [41]. Another
signicant merit of CNT application in the MMMs is to improve the
mechanical stability of the membrane. Wong et al. [90] reported a signicantly improved mechanical strength and durability of MMMs fabricated by incorporating MWCNTs into an electrospun polyvinyl alcohol
(PVA). Simultaneously, enhanced water ux has been observed as an
attribute of frictionless nanotube channels.
Gethard et al. [91] have created a novel architecture in producing a
better performance membrane for membrane distillation desalination by immobilizing MWCNTs in the pores of hydrophobic PVDF
membranes. The presence of CNTs that serve as a sorbent to provide
an additional pathway for solute transport has favorably altered the
watermembrane interactions to promote vapor permeability while
preventing liquid penetration into the membrane pores due to the
high hydrophobicity demonstrated by the MWCNTs. A profound
increase in the vapor permeation has resulted in the dramatic increase
in both salt rejection and water production. Fig. 7 schematically depicts
the transport and separation mechanism of MD process with the
presence of CNTs. Compared to conventionally used MD membrane,
the CNTs/PVDF MMMs can facilitate MD process at a relatively lower
temperature and higher ux that was six times higher. It also exhibits
greater acceptability for high saline concentration up to the equivalent
of seawater. The capability of CNTs/polymer to perform high salt
rejection has been demonstrated by Shawky and co-workers [92]
where MWCNTs were incorporated into aromatic polyamide to form a
nanocomposite membrane through a polymer grafting process. The
even distribution and dispersion of MWCNTs in the polymer matrix
have been evidenced through the SEM images as presented in Fig. 8. It
was observed that the resultant MMMs improved the mechanical properties and demonstrated ability to reject salt with little compromise in
the water ux. The addition of MWCNTs to the 10% PA membrane
increased salt rejection by inducing structural compactness of the
MMMs through the formation of network structure via strong interaction between MWCNTs and PA matrix.
Recently, a patent described on the CNT incorporated TFC membrane has been disclosed by Ratto et al. [93]. The open ended CNTs
with narrow diameter of about 0.8 nm were embedded onto the
selective layer formed by conventional interfacial polymerization on a
microporous polyethersulfone support as shown in Fig. 9. When the

Fig. 8. The FESEM micrographs evidenced the uniform distribution of MWCNTs in the polymer matrix at A) 5 mg/g and B) 15 mg/g loading of MWCNTs [92].

P.S. Goh et al. / Desalination 308 (2013) 214

Fig. 9. Schematic cross-section of CNTs incorporated to the barrier layer of the TFC
membrane [93].

MMMs were adopted to an RO system, the thickness of the layer is

substantially less than the average length of the CNTs to allow the
nanotubes to be randomly oriented throughout the matrix while providing channels extending through the layer for the selective passage
of water, hence resulting in a nearly doubling water ux compared to
that of without CNTs and a slight increase in the salt rejection from
96.2% to 97.7%.
4.3. Carbon nanotube electrodes
The major research efforts in electrode-based desalination advancement emphasize on synthesis of hierarchical micro- and nanostructured electrodes to achieve high surface area required for the
electrosorption of a signicant number of ions [72]. The interests on
CNTs as electrode materials are majorly due to the high ratio of surface
area to volume and excellent electrical conductivity compared to other
conventionally used electrode materials [94]. Additionally, other unique
features such as low resistivity, high intensity and high stability are also
some of the interesting contributions to the increasing use of CNTs as
electrode materials [95,96]. Computational studies using molecular
dynamic simulation have demonstrated that charged CNTs can be applied as nanoelectrode for ion separation in salt solution in nanoscale
lab-on-a-chip system [97]. During the desalination process, the different magnitude of applied electrical charge has resulted in different
degrees of ion separation, hence the efciency of the desalination
process. The observations have indicated that a charged CNTs can be
exploited to separate and encapsulate ions in order to promote the
desalination process in which the ion separation performance can be
quantitatively modied by varying the CNT surface charge density.
Zhang et al. [98] investigated the desalination performance of
MWCNT electrode in ow-through capacitor (FTC). They have found
that the surface modication of MWCNTs with nitric acid is one of the
most critical steps in the use of MWCNTs as electrode. The treatment
showed great effect to render high surface area and pore volume of
the nanotubes due to the elimination of undesired metal catalyst and
carbonaceous materials, which in turn inuence the amount of NaCl
removal during the desalination process. It is also concurrently found
that the when coupled with activated carbon (AC), the composite electrode demonstrated removal efciency of salt from seawater above
90% as well as highly efcient regeneration characteristics, hence the
energy consumption can be reduced by about 67% compared to conventional AC electrode [99]. In another recent study where carbon fabric
supported magnetide MWCNT nanocomposite based supercapacitor
was applied for desalination, the authors [100] pointed out that the
nanocomposite electrodes offered high salt removal efciency and
good cyclic repeatability to effectively remove multimetal impurities
and ions in a seawater desalination.
CNT sponges prepared by chemical vapor deposition (CVD) that
are composed of interconnected CNTs with the mixture of porous
structures ranging from meso- to macroporous exhibit morphological

11

advantages over the activated carbon electrode. The well retained

CNT conductivity, exibility and monolithic continuous three dimensional porous framework have promised them as an effective electrode
materials for CDI desalination to display effective ion capture capability.
In their recent work on the CDI of salt solution using CNT sponge electrodes, Wang et al. [101] have concluded that the monolithic exible
crystalline structure of the CNT sponges is the main contributor to
their superior ion removal capacity during the desalination process. As
the pristine CNT sponge bulk can be easily pressed into a exible electrode without the aid of additives as shown in Fig. 10, the possibility
of the pore blockage and the conductivity interference due to the presence of additives can be greatly minimized. This has promised the well
retained total surface area and conductivity which is benecial for the
desalination capacity. However, further experiments are highly desired
to investigate the thermal dynamics and stability of CNT sponges for
practical application in CDI.
By exploiting the high aspect ratio and other unique properties of
CNTs, Li et al. [102] produced CNTcarbon nanober (CNF) composite
lm through low pressure and temperature thermal CVD that can be
served as CDI electrode for their potential application in MCDI device.
The CNTCNF fabricated was found entangled with a cross-linked
nanotubular structure which has been suggested to favorably permit
easy access for ions to the electrode surface. Besides that, the defects
formed in the composite lm increased the ability for the accumulation of charges, which may be benecial for charge transfer in the
electrosorption process. With the advantages shown, CNTCNF has
been proposed as a high salt removal efciency as much as 49.2% compared to ordinary CDI system, as well as low cost and energy consumption material for water desalination.
In their very recent work, Nie et al. fabricated MWCNT lms for CDI
electrode using electrophoretic deposition technique [103]. They observed the entanglement of CNTs to form a microstructure network
with many mesopores that can provide more tunnels for the entering
of the solution and facilitate the migration of hydrated salts onto the
surface of the lm. In order to enhance the efciency of the electrode,
the CNTs were rst incorporated in polyacrylic acid (PAA) that served
as the cation-exchange polymer [104]. The CDI unit based on CNT
PAA composite lm electrode exhibited promising NaCl removal of
about 83%, which was 50% higher than that of using pure electrodes.
The concept of CNTs/polymer composite has also been applied by Yan
et al. [105]. They reported high ion electrosorption capacity in CDI desalination that utilized electrodes with SWCNTs incorporated into
polyaniline (PANI). Faster charge transport between the salt solution
and electrode interface has been achieved, primarily due to the facilitated electron delocalization in the PANI backbone under the inuences of
the aromatic structure of SWCNTs. Besides showing excellent recyclability and efcient regeneration, the salt removal efciency of the system was improved by 12% compared to that of the SWCNT electrodes.
5. Current hurdles and future challenges
Application of CNTs is of tremendous advantage in the eld of
desalination. Recent advancement makes realistic to afrm that CNTs
might be one of the most reliable solutions to lower the energy consumption to enable more sustainable development of desalination
technology. It can be foreseen that, in the short future, they may compete successfully with the existing desalination technology. However,
several critical issues still remain opened. One of the most critical challenges which may hinder their further development is associated with
their synthesis and processing [106]. Although the above-discussed
computational and experimental studies have provided substantial
evidence that CNTs can be used to fabricate high-ux and high selectivity membrane, it is generally difcult to synthesize CNTs with well
controlled diameter and length. In fact, the true revolutionary potential
of CNTs lies in the diverse pathway for tailored manipulation of CNT
surface chemistry. The development of innovative approaches for the

12

P.S. Goh et al. / Desalination 308 (2013) 214

Fig. 10. A) Macroscopic structure, B and C) SEM and D) TEM of CNT sponge produced from CVD [101].

novel synthesis and processing of CNTs is therefore highly desired to

make this material function more effectively in desalination application.
While lacking in experimental desalination performance data, transport
and separation properties derived from computational simulation and
prediction could serve as a stimulant for the continuous exploration of
CNTs in desalination technology. However, it is important to bear in
mind that the intact non functionalized nanotube will always remain
as a computational fantasy. In reality, the existence of ideal CNTs is
almost impossible due to the inconsistency and uncertainties of the
production. Moreover, in order to harness the exceptionally smooth
channels of CNTs for fast water transport, the CNTs must be uncapped
in which their tips are likely to be chemically modied. This might in
turn result in the loss of the CNTs' favorable transport characteristics.
Therefore, the further understanding on the inuences of various
forms of functionalization on the potential application of CNTs in
desalination is of great importance for the future development of this
technology.
Another major hindrance to the readily usage of CNTs in desalination technology is its costs and operational issues. As the manufacturing
cost of CNTs with the additional cost for the pre-treatment of CNTs prior
to its application might impose a signicant cost to the overall desalination process, the combined savings beneted from the enhanced ux
and salt rejection must be evidenced or the application of CNTs in desalination will remain economically unfavorable. Additionally, despite the
exotic predictions made, the lack of experimental desalination performance evaluation for the fabrication of CNT membranes or electrode
by scalable approaches has impeded their viability for desalination
technology. Moreover, the integration of this material into large area
membranes and measurement of the transport characteristics remain
the main hurdle. Challenges arise when scaling up the technology
from lab-scale to industrial level processes. Therefore, the platform for
experimentally verifying these predictions is in urgent need. However,
it is strongly believed that, the scale-up issue will be resolved over
time if the performance enhancement proves practically achievable.
Although much attentions have been focused on the potential
benets of water-desalination materials that have incorporated with
CNTs, there is also a need for more research to assess the potential

human health and environmental risks. Despite the many benets

and potentials they have offered, on the dark side, CNTs might also
bring about drastic safety and environment impact. Due to the increasing potential widespread use and investments, CNTs may spread
quickly to the environment. Release of CNTs into the environment is
another major concern at this point. Evidence for toxic effects of
these engineered particles has been observed on model organisms
[107,108]. Studies have also suggested that CNTs show strong interactions with heavy metal ions and organic compounds due to their
surface functional groups and hydrophobic surface [109]. Therefore,
the effects of CNTs on common environment contaminant need to
be evaluated. To safeguard the sustainable use of CNTs in desalination
technology, the unique properties of CNTs must be developed and
utilized within a sustainable framework to minimize the environment
implications.
The main question that may confront in the consideration of the role
and impact of CNTs in desalination is probably the possibility and practicality of this material to offer greater avenue for the efcient desalination. So can this emerging nanotechnology really help to mitigate the
issues related to water desalination? There is still a long way to go to
fully explore and develop this material, especially with the exciting
new properties that can be discovered through this fascinating material.
It will continue to generate interest in desalination research at both fundamental and applied levels. Therefore, the answers will only emerge
after the prediction and bench-scale studies are translated into the
real eld applications.
6. Conclusions
This review provides an overview of application of CNT materials
as the future research strategies and directions to meet the challenges
that are facing the worldwide application of desalination technologies.
In the past decades, desalination and wastewater reclamation processes
have been studied extensively to mitigate the water crisis. A suite of
new technologies is realized by recent progress in the rational design
and manipulation of nanomaterials. The CNT-incorporated desalination
materials deserve greater research efforts. Remarkable accomplishment

P.S. Goh et al. / Desalination 308 (2013) 214

of CNT-based desalination leads to greener process which could make

the desalination economically competitive to provide potable water
where it is needed. The higher ux and salt rejection have practical impacts as they eventually lead to signicantly higher efciency processes,
thus requiring less membrane materials and energy per unit of water
desalined. It is anticipated that the emergence of CNTs could revolutionize the desalination technology sector by providing higher throughput
and more effective separation characteristics, without imparting significant cost to the overall desalination system.
Tremendous interest in CNT-based desalination is evidenced from
the plethora of studies, in experimental and theoretical means, that
have implied the extraordinarily high water ux while exhibiting
promising salt rejection properties. In broader terms, the involvement
of CNTs in the desalination devices can be done through the preparation
of free standing aligned CNT membrane as well as the CNT incorporated
mixed matrix membrane. The development of such membranes is still
at the premature stage and many problems are yet to be resolved
while more challenges are awaiting. On the other hand, in nonmembrane desalination technologies, CNTs have been widely utilized
as the electrode materials. Up to date, more experimental studies have
been reported on the potential application of CNTs to enhance the
efciency of electrochemical-based desalination primarily due to the
simplicity of electrode preparation. Despite the relatively short period
of its research history in both scientic and technological aspects, the
desalination technology based on CNTs is now emerging from the laboratory or pilot scale to become a valid and reliable commercial technology. But making the leap to commercial applications is complicated and
is still a distant goal for this emerging approach. Since the commercialization of CNT-incorporated desalination technology is still at its premature stage, more scientic and technical inputs are crucial to explore
more possibilities and potentials that lie behind. Also, with the stimulating community's fascination and further impressive progresses done on
CNT material for desalination application, it has no doubt that CNT
materials will nd their role in the future direction of desalination technology to allow for greater exibility and broader perspective in
addressing the critical water issues.
Acknowledgment
The authors would like to express gratitude to the Ministry of
Science, Technology and Innovation Malaysia for the nancial support
on the work undertaken in this research center.
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