Environ Chem Lett (2017) 15:643–671
DOI 10.1007/s10311-017-0653-z
REVIEW
Carbon nanotube- and graphene-based advanced membrane
materials for desalination
Raghavendra S. Hebbar1 • Arun M. Isloor1 • Inamuddin2,3,4
Received: 11 June 2017 / Accepted: 3 July 2017 / Published online: 4 September 2017
Ó Springer International Publishing AG 2017
Abstract The development of membrane-based desalina-
tion and water purification technologies offers new alter-
natives to meet the global freshwater demand. Rapid
advancement in carbon nanotube-based and graphene-
based nanomaterials has drawn the attention of scientific
investigators on various desalination technologies. These
nanomaterials indeed offer advantageous structure, size,
shape, porosity and mass transport behavior for membrane
separation process. This article reviews theoretical and
experimental investigations of carbon nanotube- and gra-
phene-based composite materials for desalination. Special
attention is given to the simulation of molecular transport
through these materials. Further, recent advances in the
application of functionalization of carbon nanotube- and
graphene-based materials for salt rejection and hydraulic
permeation properties are discussed.
& Arun M. Isloor
isloor@yahoo.com
& Inamuddin
inamuddin@rediffmail.com
1
Membrane Technology Laboratory, Department of
Chemistry, National Institute of Technology Karnataka,
Surathkal, Mangalore 575 025, India
2
Chemistry Department, Faculty of Science, King Abdulaziz
University, Jeddah 21589, Saudi Arabia
3 of utilization, without extra stress on our environment or
Centre of Excellence for Advanced Materials Research, King
Abdulaziz University, Jeddah 21589, Saudi Arabia
4 The interest for clean water is intensifying quickly because
Advanced Functional Materials Laboratory, Department of
Applied Chemistry, Faculty of Engineering and Technology,
Aligarh Muslim University, Aligarh 202002, India
• Abdullah M. Asiri2,3
Keywords Desalination  Carbon nanomaterial-based
membranes  Carbon nanotubes  Graphene  Molecular
transport  Hydraulic permeation  Water
Introduction
Global challenges such as pollution, resource depletion,
increasing demand for food and water and changing cli-
mate conditions are forcing us to move toward the de-
velopment of a sustainable society. A standout issue is
inadequate access to safe drinking water and sanitation
(Shannon et al. 2008). It is assessed that there is an
insufficient amount of freshwater to access all present
and foreseeable human needs since water has not been
equally distributed around the globe. Only 3% of water
on earth is available as freshwater out of which 75% is
inaccessible as it is in the form of polar ice caps and
glaciers and 14% is present in deep earth crust beyond the
easy access; 11% as groundwater, 0.35% in lakes and
0.03% in rivers are easily available for human use. There
is precisely the same amount of water on earth today as
there was in the age of dinosaurs, in the age of Roman
times when the population was in just a few million and
will continue to be the same when the population will
touch 8 billion by 2020 as per current predictions (Shenvi
et al. 2015).
The lack of freshwater over the globe has made us
advance more proficient, viable, low-cost and robust
strategies to clean and purify water from source to the point
endangering the human well-being by the treatment itself.
of the total populace development that forces bigger
requests of safe water for residential, farming and industrial
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use (Liu et al. 2017). Both advancement and industrial-
ization have expanded the number of pollutants entering to
freshwater sources making a few negative medical issues.
Besides, water can likewise firmly influence food produc-
tion, energy, nature of environment and economy of the
nations. Tending to these issues gets out for a colossal
measure of dynamic research to be directed keeping in
mind the end goal to find the novel powerful, supportable,
safe water purification technology with less energy uti-
lization. At present, membrane-based separation process
has become one of the unconventional technologies for
resolving the immense challenges faced by mankind.
Compared with conventional water purification technique,
the membrane-based separation process is an environ-
mentally friendly and energy-efficient technology. More-
over, this system can be operated in combination with the
conventional methods and or on its own (Altintas et al.
2016). An ideal membrane should have controlled pore
size, higher hydraulic permeation rate with lower operating
pressure, higher selectivity and chemical resistance toward
a wide range of pHs. In addition to this, decrease in
thickness and modification of physicochemical properties
of the membrane is also essentially contributing to improve
its performance.
Desalination is one of the emerging and promising
technologies to cater global water crisis. It offers effective
removal of minerals and salts from brackish or seawater
to achieve pure water for industrial, domestic, agriculture
and human consumption (Chandrashekara and Yadav
2017). In the recent years, several technologies have been
progressed in this regard which includes mechanical
vapor pressure compression, distillation, multieffect dis-
tillation, multistage flash distillation, membrane-based
electrodialysis, nanofiltration and reverse osmosis pro-
cess. Compared to other water purification techniques,
more than 50% of reverse osmosis-based desalination
plants were installed around the world due to low opera-
tional cost, no phase change during the process and less
energy consumption compared to distillation and other
thermal-based water purification techniques (Giwa et al.
2016). According to Humplik et al., main advantage of
intensifying the membrane-based desalination technology
is that energy requirement for the multieffect distillation
process is about 26.4–36.7 kWh, for multistage flash
distillation technology requires 23.9–96 kWh and only
6.0–5.7 kWh for reverse osmosis-based technology per
cubic meter of freshwater, which incorporates pre-treat-
ment, water transport and brine disposal. At the same
time, it does not consist of the cost of infrastructure and
maintenance for large-scale production (Humplik et al.
2011). To experience the worldwide request of freshwater
shortage, the aggregate cost of desalination process must
be decreased, which incorporates upgrading the energy
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Environ Chem Lett (2017) 15:643–671
efficiency, bringing down of cost involved for water pre-
treatment and declining the capital expenses. The recent
survey stated that a steady increase in demand of mem-
brane-based desalination market is observed throughout
the globe due its advantage and advancement in the pro-
duction of low-cost pure water. In addition to this, Global
Water Intelligence and International Desalination Asso-
ciation revealed that installed desalination plants around
the world have the capacity to produce more than 19.8
billion gallons freshwater per day. The membrane and
desalination-based industry is a vast portion worth bil-
lions. The current desalination market trend is presented
in Fig. 1. The noticeable membrane fabricating organi-
zations, such as Toray, CSM, Koch Membrane Systems,
Dow-Filmtec, Hydranautics (Nitto Denko) and GE
Osmonics, cater the demand of freshwater crisis (Shenvi
et al. 2015).
Nanomaterials in water desalination
The polymer and nanocomposite materials have drawn
significant attention of many researchers for potential
development in desalination of seawater and brackish
water due to excellent selectivity, permeability, chemical
resistance toward a wide range of pH and reliable pro-
cessing strategies. A number of inorganic nanomaterials
such as zeolite, ZnO, TiO2, SiO2, metal–organic frame-
work, nanoclay materials have been utilized for the man-
ufacture of nanocomposite membrane to enhance the
physicochemical properties and execution (Qadir et al.
2017). Among them, carbon nanotube- and graphene-based
nanomaterials are reflected as the most potential and
prominent contenders for the advancement of membrane
separation process (Ong et al. 2016). Based on the Scopus
database, the list of publications related to the applications
Fig. 1 Market for desalination technology, as per the survey and
estimation made by Global Water Intelligence survey. The freshwater
production from membrane-based technology increases significantly
over the years. It is also estimated that trend is going to increase
drastically in upcoming days. Source Desaldata.com
Environ Chem Lett (2017) 15:643–671 645

of carbon nanotube- and graphene-based nanomaterials is rejection through size exclusion principle and transport of
presented in Fig. 2. water molecules. The particular and quick transport of
In particular, carbon nanotube-based nanocomposite liquid seen in carbon nanotubes has soon lighted various
membranes engrossed considerable growing interest due to continuous logical talks and researches to make utilization
potential selectivity and durability. The inclusion of carbon of this unique feature (Ma et al. 2017). In addition to this,
nanotubes into membrane matrix offers a substantial some simulation investigations and experimental evidence
advance for the desalination process. According to the proved that water can undoubtedly go through the tight
literature, high permeability rate and selectivity of carbon empty channels of carbon nanotubes. The facial and ver-
nanotubes are due to hollowed structure that can encourage satile chemical modification offered by the carbon nan-
the transport of water through channels. The schematic otubes further facilitates the enhanced flux and selectivity
representation of the movement of water molecules of the resultant membrane without destroying or altering
through carbon nanotubes is presented in Fig. 3. The small the structure and properties of nanotubes. It has also been
diameter of hollowed structure and capillary action found that the presence of carbon nanotubes can favorably
behavior have the crucial role in the implementation of ion offer the effective antimicrobial properties to mitigate the
biofouling during prolonged period of filtration (Goh et al.
2016). By virtue of this, carbon nanotube-based mem-
1 branes give the impression to be an appropriate contestant
2 2
2 that holds very positive perspective and easily adapt-
able for commercial use to encounter the current
2 drawbacks.
1 1 1 As the most up-to-date part of the group of carbon-
1 1 2 2 based nanomaterials, preparation of graphene and its
1 subsidiaries broader potential applications for desalina-
tion and another purification process. This is because of
2
1 its exceptional surface properties, vast surface territory,
2 structural characteristics, high tensile strength, negligible
2 thickness, charge density and mechanical strength (Dervin
et al. 2016). The progression in molecular simulation
studies of graphene-based materials provides the scientific
evidence for interaction and transport of water molecules
with exfoliated graphene and its derivatives (Fig. 4).
Additionally, the presence of the large surface area can
Fig. 2 A number of publications in various journals related to the easily offer a broad spectrum of functionalization and
applications of carbon nanotube- and graphene-based nanomaterials.
surface modification. Moreover, it forms hybrid
The graph could clearly indicate the versatility and applicability of
carbon nanotube- and graphene-based nanomaterials membrane- nanocomposite and complex with various nanoparticles.
based applications. Source Scopus database Various investigations have confirmed that nanoporous

Fig. 3 Pictorial representation

of movement of water
molecules through carbon
nanotubes. It represents the
selective transport of water
molecules through the hollow
channels of carbon nanotubes
membranes for desalination
applications. Source Claire Loe

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Fig. 4 Selective transport of molecules through the graphene-based
membranes (Liu et al. 2015). The porous graphene oxide and
assembled laminated graphene have the capacity of selective transport
of species across the membrane, which enhance the applicability of
graphene-based membranes for desalination. Reproduced with per-
mission of the Royal Society of Chemistry, 2015
graphene-based membrane materials provide tunable
surface properties which can offer high hydraulic per-
meation rates, selectivity, lower transport resistance and
high salt rejection. Mahmoud et al. (2015) stated that
graphene nanosheets have the adequate mechanical
strength to withstand high pressure and excellent
physicochemical characteristic in favor of effective
desalination process in spite of its negligible thickness.
Despite immense theoretical assurance, there remains a
most important hurdle to attain scalable and cost-effective
preparation of large-scale graphene and its functionalized
derivatives for membrane applications.
The point of this work is to convey a far-reaching dia-
gram of the pertinent advances and utilization of carbon
nanotube- and graphene-based nanomaterials for desalina-
tion applications. The detailed discussion of importance,
applicability and advancement of carbon nanotube- and
graphene-based nanomaterials for desalination applications
was taken place one by one.
Role of carbon nanotubes in water desalination
The emerging nanoscience and technology have gone
through splendid revolution by achieving a novel standard
in carbon nanotube-based nanomaterials for present tech-
nologies such as desalination, catalysis and sensors. The
properties and applicability of carbon nanotubes were
extensively investigated since they have been confirmed as
a predominant candidate for improving the efficacy of
presently existing desalination method (Ashraf et al. 2016).
For this purpose, a tremendous amount of research has
been conducted in finding out the various possibilities and
opportunities of carbon nanotube-based membranes to
further improvement in the desalination technique. Thus,
inclusion and novel functionalization carbon nanotubes
offer innovative methods to forms emerge as a viable and
attractive methodology for the next-generation desalination
technologies.
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Environ Chem Lett (2017) 15:643–671
Basics of carbon nanotubes
Carbon nanotubes are the outstanding class of carbon
nanomaterials first found in 1991 by S. Iijima’s group and
researched broadly from that point forward. The little
measurement carbon fibers were prepared through the
carbon vapor to developed carbon filaments by the disin-
tegration of hydrocarbons at a high temperature in the
presence of transition metal catalyst particles (Iijima and
Ichihashi 1993). Carbon nanotubes have been developed
with a sheet of carbon atoms that are rolled smooth hol-
lowed structure with one-atom thickness and have the
diameter of less than 1 nm. These barrel-shaped carbon
nanotubes have exceptional functional and structural
properties, for example, elasticity, electrical and mechani-
cal attributes, which are significant for nanotechnology,
separation, desalination and different fields of materials
science and innovation. Additionally, carbon nanotubes
have been prepared and broadly examined so as to com-
prehend the physicochemical conduct of multiwalled car-
bon nanotubes and single-walled carbon nanotubes, which
are essentially relied upon a number of carbon atoms pre-
sent in the array of empty tubular structure. Figure 5 shows
carbon nanotube and properties (Zhao and Stoddart 2009).
The most striking of these hypothetical improvements was
the forecasts that carbon nanotubes could be either semi-
conductor or metallic relying upon their geometrical
characteristics, in particular, their breadth and orientation
concerning tubular axis (Das et al. 2014).
Water transport in carbon nanotubes
The selective transport of water molecules through highly
hydrophobic and smooth inner core of carbon nanotubes
has been extensively studied as a model system, particu-
larly nanofluidic and desalination technology point of view.
It basically depends on the nanoconfined interactions of
water molecules with the inner surface of nanotubes.
According to the literature, the structure of carbon nan-
otubes has the capacity to mimic some biological pores in
light of their closeness in hydrophobic nature, tubular
structure and very small diameter. The movement of water
through carbon nanotubes signifies a unique transport of
nanofluidic dynamic approach and it illustrates the rela-
tionship between fluid and water transport through chan-
nels in the biological system (Corry 2008). It has been
reported that weak interaction of water molecule with a
hydrophobic inner core of carbon nanotubes and structural
simplicity offer a frictionless moment of water, thereby
enhancing the hydrodynamic permeation rate. Majumder
et al. (2005) reported that high-velocity transport of water
molecules from 9.5 to 43.0 cm s-1/bar was carried out
through a 7-nm-diameter membrane pore. The permeation
Environ Chem Lett (2017) 15:643–671 647

Fig. 5 Schematic
representation of a multiwalled
carbon nanotubes, b single-
walled carbon nanotubes and
properties of carbon nanotubes.
Reprinted with permission of
Das et al. (2014), Copyright
2014, Elsevier

rate was four to five times faster than conventional fluid
flow (between 0.00015 and 0.00057 cm s-1/bar). Goh et al.
(2013) specified that high water or any fluid flux rate
through the carbon nanotubes is due to the molecular
ordering phenomena of the carbon nanotubes walls and
atomic-scale smoothness inside the nanopores. In addition
to this, the transport phenomenon of water strongly
depends on the shape of the pore and curvature of the
surface. The physicochemical properties of any solid sur-
faces have predominant role in the moment of fluid and
transport behavior, as they not only influence the normal
stress by changing the density parameters in the course
normal to the interface (Fig. 6) but also offer the variation
in the lateral stress, due to the variation in adsorption
phenomenon (Goh et al. 2013). The transport phenomena
and density distribution of fluids over narrow, confined,
small diameter carbon nanotubes is an essential and
prominent issue since large variation in the properties of
water varies with different environmental conditions.
The stimulating investigation has been employed to
predict and evaluate the interaction of water or fluid
molecules with carbon nanotubes under different experi-
mental parameters. The obtained theoretical information
has significant importance for the modeling and another
approach, as carbon nanotubes are used in water transport
medium, particularly desalination application (Das et al.
2014). A large number of theoretical and modeled analyses
have been reported on carbon nanotubes transportation
characteristics. The stimulating analysis was carried out
with permutation and combination of several molecular
dynamic parameters, in order to understand the physico-
chemical behavior and transport mechanisms through hol-
low carbon nanotube channels (Fig. 7). Molecular dynamic
approach revealed that water permeation rate through
hollowed carbon nanotubes could be increased to several
magnitudes as compared to other conventional porous
structure. The equation of motions obviously clarifies the
movement of water molecules through carbon nanotube-
based films as an element of time. It straightforwardly
mirrors the kinematics and dynamics of fluid or water
through emptied tubular structure (Thomas and
McGaughey 2008); dynamics demonstrates the energy and

Fig. 6 A model illustrating the

movement of water molecules
through the a carbon nanotube
channels, b carbon nanotube-
based membrane. The higher
transport of water molecules
through vertically aligned
carbon nanotubes can be
achieved compared to the
carbon nanotube-based polymer
nanocomposite membrane.
Reprinted with permission of
Das et al. (2014), Copyright
2014, Elsevier

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Fig. 7 Molecular dynamic simulation is showed using carbon
nanotube membranes. It represents the charge density across the
nanochannels of carbon nanotubes. In addition, this shows the
selective transport of species across the membrane. Reproduced with
permission from Corry (2008). Copyright 2008, American Chemical
Society
forces, while kinematics clarifies starting velocity, dis-
placement, acceleration and time of the flow of water
through the carbon nanotube structure. Frequently it takes
after Fick’s first law of diffusion, which depicts all
movements in a messy mass going through the carbon
nanotubes. This movement alludes as the Fickian move-
ment. Nonetheless, it is likewise guessed that there is a
secondary passage of water molecules through the restric-
ted one-dimensional channel of the carbon nanotube. This
development takes place after a solitary document system
in which they are obstructed from crossing each other. The
diffusion of water particles through carbon nanotubes is a
very coordinated movement and is portrayed by the bal-
listic movement of water chains (Holt 2009). Fickian,
single document and ballistic movements are three unique
isotherms to portray the nature of the flow of water
molecules through carbon nanotubes and follow given
conditions:
dr 2 1 Ddt ð1Þ
dr 2 1 Fdt1=2 ð2Þ
2
dr 1 Bdt ; 2
ð3Þ
where dr 2 is the mean square displacement; D, F and B are
proportionality coefficient; and dt is time gradient. Equa-
tion (1) describes the diffusion of water molecules through
carbon nanotubes by measuring self-diffusion coefficient
(D) from the dr 2 of water molecules as a function of time.
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Environ Chem Lett (2017) 15:643–671
Equation (2) is used to get single-file mobility of water
molecules through one-dimensional channel of carbon
nanotube and is dependent on diameter of carbon nanotube,
connectivity and pore–fluid interactions. The mechanism of
water diffusion is understood by the ballistic motion
Eq. (3) with the molecules of water having negligible
interactions with carbon nanotubes. In general, water does
not follow the simple fluid mechanics. Ahn et al. 2012
replaced simple fluidics with ‘nanofluidics’ to simulate
water movement through a nanotube. The passage of fluid
through a nanosized channel can be visualized as sliding of
water molecules through the nanochannel has no effect of
friction force (Sears et al. 2010). This mechanism is
mathematically represented by Hagen–Poiseuille equation
using a slip-flow condition.
pðd=2Þ4 þ4ðd=2Þ3 :Ls ðdÞ DP
Qslip ¼ : ; ð4Þ
8l L
where Qslip is slip length of water flux into nanochannel; d
is diameter of the nanochannel; DP is pressure gradient
between the open ends of nanochannel; l is viscosity of
water; L is length of the nanochannel and Ls ðd Þ is slip
length. Ls ðdÞ can be measured by following equation:
C
Ls ðd Þ ¼ Ls1 þ : ð5Þ
d3
Carbon nanotubes have average slip length (Ls1 ) of 30 nm.
C is the fitting parameter and d is diffusion coefficient of
water molecules (0.9423 9 10-9 m2/s for a 2.1-nm-diam-
eter nanotube) (Goh et al. 2013). This mechanism is
applicable for the transport of fluid through most of the
nanochannel membranes.
One of the significant findings on transport nature and
physicochemical conduct in the wake of stacking of water
atoms into the emptied carbon nanotubes has been depicted
by Hummer et al. They expressed that nanoscale confine-
ment, in emptied carbon nanotubes channels, can prompt
lessening of the interaction energy distribution, which in
turn diminishes the free energy and chemical potential
(Hummer et al. 2001). In order to support the above
investigation, Kolesnikov et al. represented that the resis-
tance offered during the movement of water molecules
through carbon nanotubes is because of stronger inter-
molecular interaction collaboration between the water
molecules than the interactions with the carbon nanotube
walls. These results give the mechanistic understandings
into gigantically quick water entry by hypothesizing
depictions for effects of the carbon nanotube structure
alteration on the penetration rate for the transport of gasses
and fluid through carbon nanotubes channels (Kolesnikov
et al. 2004). Development of carbon nanotubes layers for
chemical separation and water treatment applications is
displayed in Fig. 8.
Environ Chem Lett (2017) 15:643–671
Fig. 8 Schematic representation of advancement of carbon nanotube-
based membranes in water treatment and another separation process
(Mauter and Elimelech 2008). The rapid growth of carbon nanotube-
based membrane materials for the effective desalination and water
Functionalization of carbon nanotubes
for desalination
The theoretical transport phenomenon of hollow carbon
nanotubes was often proved by studying the water transport
through individually isolated and ideal carbon nanotubes.
The hypothetical transport phenomenon of hollow carbon
nanotubes was regularly demonstrated by studying the water
transport through separately isolated and perfect carbon
nanotubes. In any case, preparation and processing of in
place carbon nanotubes remain a major challenge. In reality,
fabrication of such defect-free ideal membrane is extremely
difficult and not feasible for practical applications. Mauter
and Elimelech (2008) agglomeration in the carbon nanotube-
based films offers a quick upgrade of water saturation rate,
yet in the meantime diminishes the selectivity and rate of salt
dismissal properties. In general, prepared single-walled car-
bon nanotubes and multiwalled carbon nanotubes will have
the trace amount of metals, defects, catalyst contaminations
and other physical heterogeneities. An essential parameter to
take care so as to advance in desalination technology is to
overcome the hurdles of processing, get rid of impurities and
uniform distribution in the membrane matrix due to their
agglomeration trend rather than intact and isolated carbon
nanotubes. Moreover, when pore distance across of nan-
otubes is 1 nm, it would prompt an extensive variety in free
energy hindrance brought on by the shedding of hydration
shells of ions and water molecules. Therefore, surface
functionalization is important to adjust the physicochemical
properties so as to decrease the energy hindrance. In partic-
ular for desalination applications, ionic radius of salts with
hydrated form will be *0.358 nm, and to achieve superior
649
treatment applications is due to its stringent selectivity and higher
permeability. Multiwalled carbon nanotube (MWCNT), carbon
nanotube (CNT). Reproduced with permission from Mauter and
Elimelech (2008). Copyright 2008, American Chemical Society
salt rejection efficacy, the pore size dissemination of the
carbon nanotubes must be particularly narrowed; hence,
additionally entangled and precisely controlled preparation
conditions are basic which stays as a generous test for broad
utilization of carbon nanotubes in desalination (Ahn et al.
2012). Meng et al. (2009) expressed that tips carbon nan-
otube with higher reactivity can be additionally oppressed to
specifically functionalize to bring about basic assorted
qualities and exceedingly tailor-made material.
The functionalization of carbon nanotubes via chemical
modification methods offers the effective way to improve
the water permeation, controlled fluid transport and selec-
tivity. According to the literature, it was noticed that
preparation and chemical modification have been widely
considered and compressed in a few review article (Ih-
sanullah et al. 2016; Goh et al. 2013; Meng et al. 2009).
Technological improvements to overcome the above-
mentioned hurdles consist of modification of tip of the
nanotubes to improve the surface hydrophilicity and
selectivity. The inclusion of hydrophilic polar functional
groups into the surface of carbon nanotubes increases the
electrostatic interaction and binding energy between nan-
otubes and water molecules, hence facilitate permeation
rate (Fig. 9). Grafting of steric functional groups over the
tip of large diameter nanotube pores put forward a stimu-
lating approach to improve the selectivity and salt rejection
capacity. Generally, modification of carbon nanotubes was
carried out through three different approaches, namely
(a) Chemical modification to obtain tip-functionalized
carbon nanotube membrane
(b) Chemical grafting along carbon nanotube axis for
core-functionalized membranes
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Fig. 9 Schematic representation of a chemical modification of
carbon nanotubes tip and core channel through grafting. The presence
of polar functionality at the tip of carbon nanotubes enhances the
permeability and salt rejection behavior. Reproduced by permission
of Majumder et al. (2005) of the Royal Society of Chemistry
(c) Plasma-assisted oxidation of membrane with car-
boxylic acids functionality at the carbon nanotube
tips.
After the modification of carbon nanotubes, primary
investigations revealed that plausible structural change and
optimization of this material lead to substantial improve-
ment in the water flux and salt rejection efficiency. Prac-
tically, transport of water and ion selectivity through the
carbon nanotube membrane could be accomplished by
controlled interaction of ion and water molecules with
membranes after the grafting with the desired functionality
(Vatanpour et al. 2017). Therefore, several investigations
were conducted to control the pore diameter, surface
properties in order to achieve higher selectivity and flux
rate during the desalination process. The overview of
chemical modification of carbon nanotubes through dif-
ferent synthetic route is presented in Fig. 10.
Contemporary developments in fabrication of mem-
branes allowed proper arrangement of carbon nanotubes
array for better water transport. The permeation rates
through these membranes have been significantly high
compared to theoretically calculated values via simulation
investigation and hydrodynamic theories. The simulation
studies proved that transport of ion or water through a
range of pore diameter and functionalized carbon nan-
otubes allows the rapid transport of water but ions do not.
The simulation investigation by the Joseph et al. (2003)
illustrated that chemical modification of carbon nanotubes
with polar functional groups such as –COO- and –NH3?
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Environ Chem Lett (2017) 15:643–671
can achieve better anionic and cationic selectivity in the
presence of an electric field. This outcome is essential for
the unique interest to chemical modification of carbon
nanotubes with a narrow diameter, in which the presence of
charged polar functionality in the tip of carbon nanotubes is
very much essential to control water transport and exclu-
sion of very small ions for desalination applications
(Table 1). Goldsmith and Martens described the molecular
dynamic simulation study of pressure-driven transport of
water molecules and aqueous salt solutions through model
nanopores. The systematic investigation was carried out
with membrane comprising of (n, n) nanotubes of carbon
nanotubes. The experimental results demonstrated that
functionalization of carbon nanotubes provides the
improvement in water flux and salt rejection, which is
attributed to direct electrostatic interactions between the
aqueous ion solution and surface charges as well as the
effect of the water structuring induced by different charge
pattern (Goldsmith and Martens 2010). Park et al. (2006)
also carried out the similar simulation investigation com-
prising of Y-junction nanotube prepared via connecting
branched carbon nanotubes with the size of (5, 5) and (6, 6)
to a larger (8, 8) nanotubes for separation of K? and Cl-
ions from a KCl solution.
Recently, detailed investigation of water and ion trans-
port through functionalized and non-functionalized carbon
nanotubes is conducted by Corry (2011), through molecu-
lar dynamic simulation study. Figure 3 represents the effect
of polar functional groups in the tip of carbon nanotubes
for the transport of water and ions. They stated that carbon
nanotubes functionalized with negatively charged polar
functional groups such as –COO- and –NH3? offer sig-
nificant improvement in desalination efficiency since neg-
atively charged functionality prevented transport of Cl-
ions and charged groups could repel the Na?, and almost
complete rejection of both types of ions can be achieved.
At the same time, a considerable decline in the water
permeation rate was observed in modified carbon nan-
otubes due to the reduction in neutral and smooth internal
tubular structure after modification. Joseph et al. also state
the possible mechanism for declining water flux due to the
mechanically rough surface of carbon nanotubes upon
modification. In order to avoid the unfavorable condition,
steric functionalization over the tip of the carbon nanotubes
has been very effective way to improve the rate permeation
(Joseph et al. 2003). However, in spite of small flux decline
compared to non-functionalized carbon nanotubes, the
functionalized carbon nanotubes displayed flux that is
considerable than currently available polymeric desalina-
tion membranes. Fornasiero et al. reported carboxyl func-
tionalized at the tip of larger diameter carbon nanotube
array to attain prominent salt rejection efficiency via
electrostatic repulsive interaction. The presence of polar
Environ Chem Lett (2017) 15:643–671 651

Fig. 10 Overview of chemical

modification of carbon
nanotubes through different
synthetic route. The carbon
nanotubes can be easily
functionalized using different
chemical reaction under various
experimental conditions. This
showed the versatility of carbon
nanotubes for different
applications. Reprinted with
permission of Das et al. (2014),
Copyright 2014, Elsevier

Table 1 Hydraulic permeation

Tube type Flux Na? flux Cl- flux Na? rejection Cl- rejection
and ion rejection through
(%) (%)
functionalized carbon nanotube.
Reproduced by permission of Non-functionalized 107.8 ± 0.6 0.22 ± 0.01 0.05 ± 0.01 28 86
the Royal Society of Chemistry
2011, Corry (2011) 4COO- 35 ± 2 0.10 ± 0.04 0.00 ± 0.03 32 100
8 COO- 14 ± 3 0.00 ± 0.03 0.00 ± 0.03 100 100
2NH3? 60 ± 2 0.03 ± 0.03 0.03 ± 0.03 86 87
4NH3? 21.7 ± 0.7 0.00 ± 0.03 0.00 ± 0.03 100 100
8NH3? 18.9 ± 0.8 0.00 ± 0.03 0.00 ± 0.03 100 66
2NH3? 2COO- 46 ± 2 0.03 ± 0.03 0.03 ± 0.03 82 82
4NH3? 4COO- 46 ± 8 0.03 ± 0.03 0.00 ± 0.03 55 100
8OH 43 ± 2 0.08 ± 0.04 0.00 ± 0.03 50 100
4CONH2 59 ± 3 0.13 ± 0.06 0.03 ± 0.03 14 86
8CONH2 38 ± 2 0.10 ± 0.04 0.00 ± 0.03 29 100

functional groups imparts the charge to exert electrostatic
repulsion to forbid the inclusion of salt ions (Fornasiero
et al. 2008). Salt rejection of approximately 100% has been
attained, specifically for the salt solution with greater anion
valence charge such as K3Fe(CN)6 (Fig. 11). According to
the literature, it was observed that functionalization of
carbon nanotubes at the tip of nanotubes significantly
improves the water permeation with better salt rejection
capacity compared to other polymeric membranes. This
highlights understanding the effect of chemical
modification of carbon nanotubes as a potential candidate
for the fabrication of desalination membranes and further
developing this technology.
Application of carbon nanotubes in desalination
The enormous physical properties and advances made in
carbon nanotube materials promote new possibilities to
address the disputes faced by present existing desalination

123
652
Fig. 11 a Schematic
representation of –COOH
functionality at the tip of carbon
nanotubes, b salt rejection
behavior and c the Debye length
profile after the modification.
The salt rejection behavior of
the carbon nanotube-based
membranes strongly depends on
the nature charge density at the
tip of nanochannels.
Reproduced with permission of
Fornasiero et al. (2008),
Copyright Ó National Academy
of Sciences
technologies. Also, the outstanding advancement in the
molecular-level interactions of carbon nanotubes launches
the opportunity for this material to directly contribute to
excellent innovation for effective water purification and
desalination process (Wan Azelee et al. 2017). In order to
determine the effectiveness of carbon nanotube-based
membranes for the enhancement of performance, detailed
investigations of water flux and salt rejection phenomenon
were carried out. In this unit, the application and devel-
opment of carbon nanotubes for desalination process are
emphasized with attention on their opportunity to be
engineered into perspective membrane materials. The salt
rejection behavior of carbon nanotube-based membranes is
presented in Fig. 12.
Carbon nanotube membranes
The recent advancement in carbon nanotubes offers
excellent opportunities in membrane-based separation
processes due to high water flux and ion selectivity through
nanotubes. Dumée et al. (2010) reported preparation of
self-supporting carbon nanotubes buckypaper membranes
for direct contact membrane distillation. The unique sur-
face and structural properties of buckypaper exhibit a better
porosity of 90%, and the contact angle of 113° indicates
higher hydrophobicity with a thermal conductivity of
2.7 kW/m2 h. They stated that buckypaper structures are
held by van der Waals force of interactions without any
external binding agent, which was functionalized for
desalination in a direct contact membrane distillation pro-
cess to aid as the substitute that is capable of enabling some
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Environ Chem Lett (2017) 15:643–671
intrinsic drawbacks of presently existing membrane distil-
lation technology. Baeka et al. (2014) illustrated the
applicability of vertically aligned carbon nanotubes con-
taining membrane for water purification. Primarily, verti-
cally aligned carbon nanotube membranes showed better
flux performance, about three times higher than the com-
mercial ultrafiltration membrane (6.8 9 1010/cm2 of pore
density and 4.8 nm of pore diameter).
A study of water flux properties of the vertically aligned
carbon nanotube membrane compared to the ultrafiltration
membrane is shown in Fig. 13. Water transport rate is
around 70,000 times higher than the conventional flow
under non-slip environment. In addition to this, an
enrichment factor of vertically aligned carbon nanotube
membranes enhanced with increasing solvent hydrophilic-
ity, the highly hydrophobic solvent water exhibited highest
enrichment factor compared to other solvents. Hinds et al.
demonstrated the effective preparation of well-ordered
multiwalled carbon nanotube-based membranes with a
nanoporous structure. The resultant membrane showed
superior transport rate via aligned carbon nanotube cores.
Oxidative functionalization of carbon nanotubes with car-
boxylate end groups at the tip of inner core showed
enhanced flux by a factor of 15 (Hinds 2004). Tofighy et al.
(2011) extensively investigated the advantage of carbon
nanotubes containing membranes for desalination applica-
tions. They analyzed the effect of a feed comprising of salt
solution concentration 10,000, 20,000 and 30,000 ppm on
membrane performance with different experimental con-
ditions such as pressure (4, 7 and 10 bars), temperature (25,
35 and 45 °C) and flow velocity (200, 350 and 500 l/h).
Environ Chem Lett (2017) 15:643–671
Fig. 12 a Conductivity profile of 3500 ppm NaCl solution after passing through the microchannels of carbon nanotube membranes, b SEM
images of the membranes after salt rejection. Reproduced with the permission of Nature Communications 2013, Yang et al. (2013)
Fig. 13 Water flux properties of the vertically aligned carbon
nanotube membrane compared to the ultrafiltration membrane; a water
flux and enhancement factor. The hydraulic permeability of the
ultrafiltration membrane increases up to 1500 L/m2 h bar by using
vertically aligned carbon nanotubes compared other ultrafiltration
permeability of 500 L/m2 h bar. Reprinted with permission of Baek
et al. (2014), Copyright 2014, Elsevier
The result revealed that highest separation efficiency was
achieved with feed concentration, temperature and flow
rate 30,000 ppm, 45 °C and 500 l/h, respectively (Tofighy
et al. 2011). With the expanding temperature, the ion take-
up limit of carbon nanotubes improved; henceforth, the
quantity of free amassed ions around the film surface
decreased and allowed simple transport of water molecules
653
through the empty tubular cavities of carbon nanotubes.
The comparable impact could likewise be seen by
upgrading the ion feed concentration. Therefore, the
hydraulic penetration rate was enhanced without causing a
significant influence on concentration polarization effect.
Carbon nanotube-based membranes offer less energy
consumption due to frictionless fluid transport through the
vertically aligned hydrophobic hollow cavity of nanotubes
(Fig. 14). Moreover, these membranes are highly selective
toward impurities, salts, antifouling, reusable and self-
cleaning properties. The presence of these functional
groups can selectively allow the water molecules through
the tubular channels by rejecting other contaminants. In
order to substantiate the effect of functionalization, Chan
et al. (2013) conducted the simulated investigation for
carbon nanotube membranes with different experimental
parameters. The results revealed that functionalized carbon
nanotubes with two zwitterions at the end of nanotubes
exhibited nearly 100% salt rejection, whereas non-func-
tionalized membrane showed very less rejection. After the
chemical modification of carbon nanotubes, an abundant
number of polar functional groups were introduced for
effective interaction with water molecules with the surface
of nanotubes.
The several studies based on experimental and simula-
tion investigation proved the potential of carbon nanotubes
membranes, function as efficient membrane material by
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654
Fig. 14 Theoretical projection of the possibilities for aligned carbon
nanotube membranes versus permeability of membranes. The lower
permeability of thin-film composite seawater reverse osmosis was
significantly enhanced by using the aligned carbon nanotubes.
Reproduced by permission of the Royal Society of Chemistry 2011,
Pendergast and Hoek (2011)
eliminating existing drawbacks and also offer enhanced
salt rejection capacity with highest water permeation. In
general, the applicability of carbon nanotube-based mem-
branes under larger hydrostatic pressure usually involves
the carbon nanotubes to be packed inside a strong non-
porous substance to hinder them from isolating apart.
Along these lines, sealing between the tube crevices of
carbon nanotubes exhibit and end of the over the top filling
layer is the basic strides that should be mulled over during
the manufacture of carbon nanotube membranes
Fig. 15 Carbon nanotube-based membranes in the microchannel
device, which exhibits the applicability of carbon nanotubes with
tunable membranes for nanofiltration for desalination and other
123
Environ Chem Lett (2017) 15:643–671
(Pendergast and Hoek 2011). Hinds (2004) reported the
revolutionary work as mentioned in the earlier section,
preparation of silicon chip-supported and freestanding
vertically aligned carbon nanotubes, which was completed
using difficult synthesis procedure (Hinds 2004). The
ultimate objective is to prepare intact and densely packed
vertically aligned carbon nanotubes for optimization and
development of desalination application. Subsequently,
future examinations and research are basic to substantiate
the reasonableness and attainability of vertically adjusted
or freestanding carbon nanotube-based membranes in a
large-scale desalination. Figure 15 exhibits the advance-
ment of carbon nanotube membranes for macromolecule
chemical separation to tunable membranes for nanofiltra-
tion. The headway and advancement of specific, high flux
and fouling resistance membrane is expected as the future
concentration for desalination (Yang et al. 2013).
Carbon nanotubes/polymer nanocomposite
membrane
Polymer nanocomposites, in which polymers go about as
hosts for inorganic particles of nanoscale measurements,
have pulled in logical and innovative consideration in the
manufacture of nanocomposite membrane. The idea of
nanocomposite membrane was first proposed in the 1980s
to overpower the limitation of the polymeric membrane for
separation phenomenon. The nanomaterials such as TiO2,
SiO2, ZnO, zeolite have been typically employed to
immobilize in polymer phase improve the membrane
separation applications. Carbon nanotubes (CNTs). Reproduced with
the permission of Nature Communications 2013, Yang et al. (2013)
Environ Chem Lett (2017) 15:643–671
performance. The presence of these nanoparticles pos-
sesses higher selectivity and improved water penetration
rate by drawing in water molecules into the membrane
network (Ong et al. 2016; Goh et al. 2016). One of the
favorable methodologies is to make use of carbon nan-
otubes for desalination process via inclusion of these
nanotubes into membrane matrix for better separation
efficacy, mechanical strength, chemical stability, advanced
functionality and rapid water transport. Mauter and Elim-
elech (2008) stated that the presence of carbon nanotubes
into the membrane matrix disturbs the polymer packing,
therefore creates nanoscale porous cavities and aids in
enhanced water permeation rate. Moreover, incorporation
of carbon nanotubes illustrates the new degree of freedom
in the fabrication of desired nanocomposite membrane by
altering the interaction and composition of the base poly-
mer. The dispersed nanotubes effects the characteristic
properties and performance of the resultant membrane.
As discussed earlier, the tiny pore diameter of nan-
otubes allowed frictionless water transport, and carbon
nanotube-based nanocomposite polymer membrane exhi-
bits a valuable alternative in the preparation of tailor-
made membrane structure and hence imparts the enhanced
performance. In addition to this, the surface and physic-
ochemical properties such as hydrophilicity, mechanical
stability, charge density, surface roughness and porosity
of polymer nanocomposite membrane were greatly
affected by carbon nanotubes. Wong et al. (2005)
explained the variation in physicochemical and perme-
ation characteristic of polyvinyl alcohol nanocomposite
membrane by using carbon nanotubes by the electrospun
method. They stated that, after incorporation of carbon
nanotubes into the membrane matrix, durability,
mechanical strength, permeation and selectivity of the
resultant membrane were significantly improved. Gethard
et al. (2011) demonstrated an effective strategy to
improve the membrane performance for distillation
Fig. 16 Schematic
representation of the rapid water
transport through carbon
nanotube-based nanocomposite
membrane. The permeability of
nanocomposite membrane
increases because of fast
transport through the carbon
nanotube channels. Reproduced
with permission from Gethard
et al. (2011). Copyright 2010,
American Chemical Society
655
desalination process by incorporating multiwalled carbon
nanotubes into pores of hydrophobic polyvinylidene flu-
oride membrane. After inclusion of carbon, nanotubes
serve as an additional pathway for solute transport and
favorably alter the interaction between membrane surface
and water molecules, thereby enhancing the vapor per-
meability by inhibiting the penetration of liquid molecules
into the pores of the membrane matrix. Figure 16 repre-
sents the separation and transport phenomenon of mem-
brane distillation process in the presence of carbon
nanotubes. They stated that insertion of carbon nanotubes
in the membrane can potentially facilitate the transport
phenomenon by enhancing the permeation rate about six
times with considerably lower temperature compared to
conventional membrane distillation process (Gethard
et al. 2011). It also displays superior acceptability for high
saline concentration up to the equivalent of seawater.
Furthermore, Shawky et al. (2011) also illustrated the
applicability of carbon nanotubes/polymer nanocomposite
membrane for better salt rejection and permeation prop-
erties. The modification of carbon nanotubes was carried
out via grafting of aromatic polyamide and incorporated
into membrane matrix. The mechanical strength of
nanocomposite membrane is increasing with increasing
carbon nanotubes dosage and showed increasing tensile
strength, toughness and Young’s modulus (Shawky et al.
2011). The presence of carbon nanotubes enhanced the
rejection behavior of both organic matter and salt relative
to the 10% compared to pristine polyamide membrane.
The both experimental and simulation analyses illustrated
that polymer nanocomposite with functionalized carbon
nanotubes was predominantly employed to fabricate highly
proficient desalination membrane. The simulation investi-
gation conducted by the Chan et al. reported that the pres-
ence of zwitterion functionalized at the tip of nanotubes
offers higher hydraulic permeation by essentially rejecting
all the ions. The modified carbon nanotubes were partially
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656
aligned in a polyamide layer through a high-vacuum filtra-
tion step during the membrane preparation. The pure water
permeation was found to be enhanced by more than factor 4,
i.e., from 6.8 to 28.7 gallons per square foot per day, as the
concentration of functionalized carbon nanotubes was
enhanced from 0 to 20 wt% salt rejection capacity improved
considerably from 97.6 to 98.6% (Vatanpour et al. 2014).
Similarly in other work, amine-functionalized multiwalled
carbon nanotubes were employed as an additive for the
preparation of polyethersulfone nanocomposite membrane
to improve the physicochemical properties and performance.
The resultant membrane exhibited higher hydrophilicity,
porosity, surface roughness and water flux with the addition
of 1 wt% of additive dosage (Choi et al. 2006). Choi et al.
(2006) investigated the effect of functionalized carbon
nanotubes on morphology and surface wetting characteristic
of polysulfone nanocomposite membrane. The addition of
carboxylic acid-functionalized carbon nanotubes exhibits
higher hydrophilicity, and cross-sectional morphology was
dependent on the quantity of modified carbon nanotubes
used during the membrane preparation (Zhao et al. 2013).
Recently, Zhao et al. (2013) developed the highly efficient
polyamide reverse osmosis membrane by immobilization of
carboxyl-functionalized carbon nanotubes. The nanocom-
posite membrane presented more negative charge density
and higher hydrophilicity compared to pristine polyamide
membrane (Zendehnam et al. 2014; Ihsanullah et al. 2016).
It was interesting to note that change in the morphological
features, porosity and other surface properties favors to
increase the pure water flux and salt rejection ability. Fur-
thermore, modified membrane displayed superior antiox-
idative and antifouling properties compared to non-
functionalized carbon nanotubes polyamide nanocomposite
membranes. The overview of the application of carbon
nanotubes in desalination is presented in Table 2.
Challenges for carbon nanotubes in desalination
Enormous attention in carbon nanotube-based desalination
process is proved from a plethora of investigation in theo-
retical and experimental studies, which have indicated the
extremely high hydraulic permeation and offered favorably
high salt rejection abilities. The potential envelopment of
carbon nanotubes in desalination technique via vertically
aligned carbon nanotubes membranes and fabrication of
polymer nanocomposite membranes enhances the perfor-
mance efficiency. The progress of such advanced membrane
materials for desalination is still at a premature stage, and
several critical issues are yet to be resolved for the devel-
opment of the highly efficient process. Moreover, commer-
cialization of a technique always is governed by on its raw
materials costs and quality of the process. The low-cost
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Environ Chem Lett (2017) 15:643–671
carbon nanotubes with little compromising in selectivity and
rejection behavior are economically feasible for large-scale
desalination applications. Presently, chemical vapor depo-
sition strategy has been widely utilized for preparation of
multiwalled carbon nanotubes by using fluidized bed reactor
or a plug flow reactor. Nonetheless, the general quality of
these prepared carbon nanotubes could be less proficient for
desalination and water purification because of the inade-
quacy of procedure to controlling wide varieties in pore size,
length and width. Since more technical and scientific efforts
are essential to investigate, expand the potentials and pos-
sibilities (Aghigh et al. 2015). Additionally, with empow-
ering examination, interesting and further impressive
improvement was done on carbon nanotube-based mem-
brane material for desalination application. It has probably
carbon nanotube-based film materials that will discover their
role in the forthcoming pattern of desalination innovation to
take into consideration more extensive point of view and
prevalent adaptability in tending to the basic water issues.
Graphene-based membranes for desalination
Apart from one-dimensional carbon nanotubes, the recently
emerged two-dimensional graphene has pulled in critical
consideration of scientists over the globe, because of cutting
edge mass transport properties in relation to perfectly
arranged carbon atoms via sp2 hybridization. Since in the
2010 Nobel Prize for ‘outstanding contribution toward the
two-dimensional graphene material,’ there are exponentially
developing enthusiasm for centering graphene-based mem-
branes materials for separation and desalination applications.
Specific interaction of graphene and its derivatives with the
target molecules, inherent spacing, passages or channels
between the sheets have provided stimulating tools for the
development of innovative assembling for water treatment
applications (Liu et al. 2015; Perreault et al. 2015). Partic-
ularly, these graphene-based membranes with nanoscale
quantum structures show enormous potential to become the
key material for cutting edge desalination. Furthermore,
these materials offer higher mechanical strength and chem-
ical stability over a wide range of pHs, making effective for
seawater desalination at a small amount of the cost of
industry-standard reverse osmosis frameworks (Wei et al.
2014). The schematic representation of graphene and its
derivatives is presented in Fig. 17.
The simulation investigations have been proved that
single-layer graphene with nanopores structure can be
effectively employed for the desalination application with
selective ion rejection and higher hydraulic permeation.
Desalination performance strongly related to the pore
characteristic in terms of size, density, volume and chem-
ical functionalization also the working conditions. The
Environ Chem Lett (2017) 15:643–671 657

Table 2 Overview of application of carbon nanotubes in desalination

Material Water pollutant Major observation References

CNTs-co-Cu nanolayer Saline water Selectivity was improved by an increase in composite Park et al. (2014)
nanoparticles content
Mechanical stability and conductivity improved
Carboxylated CNTs NaCl The membrane was more stable over prolonged operational time Bhadra et al. (2013)
Water permeation achieved up to 19.2 kg/m2 h for 3.4% NaCl
concentration
More than 99% of the salt reduction was obtained
MWCNTs Salty water Oxidized carbon nanotubes membrane by HNO3 and H2SO4 was Tofighy et al. (2011)
very effective for salty water desalination
Maximum separation % attained was at the highest feed
concentration
MWCNTs KCl Rejection mechanism was dominated by electrostatic interactions Fornasiero et al. 2008)
K3FeCN6 between fixed membrane charges and mobile
CNTs Increased water flux of about three times faster Rahimpour et al. (2012)
Water transport approximately 70,000 times faster than
conventional no-slip flow
NH2-MW CNTs Na2SO4 and NaCl Higher hydrophilicity and smoother surface for modified Dumée et al. (2010)
membranes
0.005 wt% NH2 multiwalled carbon nanotube showed best
separation performance
Modified membrane showed improved fouling resistance
Zwitterionic CNTs Salt rejection Membranes exhibit high water flux while maintaining high salt Chan et al. (2013)
rejection
Zwitterionic functionality imparts improved membranes’
biofouling resistance
CNTs Improvement of water permeation by the optimization of aligned Roy et al. (2014)
carbon nanotube membrane
Providing a new idea to utilize carbon nanotubes membrane for
desalination
CNTs Salt water The porosity and hydrophilicity of support layer were increased de Lannoy et al. (2013)
Membrane permeability induced by carbon nanotube and active
layer etching was improved
Carboxylated CNTs Membrane distillation mode was found to be as high as 121 kg/ Vatanpour et al. (2012)
m2 h at 80 °C
The bilayered membrane represented an enhancement of 70% over
the unmodified membrane
MW CNTs Proteins Structural parameters of multiwalled carbon nanotubes Schnorr and Swager (2011)
significantly influence the mechanical strength
Mechanical stability and hydraulic permeability improved

parade of new logical examinations made in this field is
extraordinary and is considered as the ‘next enormous
things’ to offer a straightforward and feasible answer for
current obstacles in desalination technology (Sun et al.
2016). Figure 18 represents the structure and possible
application of graphene-based materials in various fields.
Most importantly, graphene oxide or chemically modified
graphene oxide can form well-ordered 2D nanochannels
between two graphene layers and offers less hydraulic
resistance via facile filtration-assisted self-assembly pro-
cess. In addition to this, one-atom thickness of these gra-
phene or graphene oxide-based materials has the ability to
form ultrathin selective barriers with highest permeation
rate and maximum separation abilities through artificially
arranged stacking structure or nanopores in the matrix
(Abraham et al. 2017).
In current years, large interest has been expressed to
understand the mechanism and investigating the possible
applications in connection with the mass transport through
graphene. According to the Sun et al. (2016), variation in
composition and structural regularity in the graphene-based
materials such as graphene oxide, functionalized graphene
oxide and nanoporous graphene offers significant variation
in physicochemical properties and mass transport behavior.

123
658
Fig. 17 Schematic representation of a graphene, b graphene oxide, c reduced graphene oxide. Reproduced with permission from Wei et al.
(2014). Copyright 2014, American Chemical Society
Fig. 18 Schematic representation of the structure and possible
application of graphene-based materials in various fields. Reproduced
with the permission of Ó 2016 WILEY–VCH Verlag GmbH & Co.
KGaA, Weinheim, Sun et al. (2016)
Recently, various review articles have been published
based on this area, which is mainly emphasizing on
preparation and characterization of graphene oxide-based
membrane materials for the particular applications such as
impermeable barrier films, desalination and pressure-dri-
ven molecular separation. Cohen-Tanugi and Grossman
(2012) demonstrated the applicability of single-layer free-
standing graphene with smaller pore diameter for desali-
nation applications by the selective rejection of sodium
chloride ions from the aqueous solutions. Simulation
investigations were proved that transport phenomenon and
selectivity of graphene-based membranes were principally
depended on the pore diameter and presence of polar
functional groups (O’Hern et al. 2014). In order to under-
stand the relationship between the potential of porous
structures and charge density on the transport properties,
O’Hern et al. (2014) reported the selective mass transport
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Environ Chem Lett (2017) 15:643–671
mechanism through single-layer graphene membranes
comprising of high-density poses with sub-nanometer
diameter. The extensive investigations on permeation and
selectivity behavior of graphene-based membranes offer
promising advantage and applications in the field of water
desalination, separation, filtration, selective mass transport,
energy storage and conversion, etc. (Ganesh et al. 2013).
Table 3 summarizes some of the important applications of
membranes other than graphene-based materials.
Basics of graphene-based materials
Prior to discussing the application of graphene-based mem-
branes, the inherent properties and preparation of graphene
will be briefly discussed. Hence, physicochemical properties
of the graphene and its derivatives have a significant influ-
ence on the membrane performance. As discussed earlier,
graphene is a one-atom thickness of sp2-hybridized carbon
atoms organized in a honeycomb structure and is considered
as the thinnest two-dimensional material (Liu et al. 2015;
Werber et al. 2016). After successful isolation of graphene
material, substantial attention has been engrossed in several
fields such as materials science, chemistry, fundamental
physics and other disciplines. In particular, the novel two-
dimensional structure and single atomic thickness along with
chemical inertness, mechanical strength, flexibility, thermal
stability and high specific surface area of graphene offer
many outstanding opportunities and applications in material
science, including desalination and membrane-based sepa-
ration. The most important derivative of graphene is gra-
phene oxide, which exhibits physicochemical properties
similar to that of graphene but differs by having many oxy-
gen-containing functional groups, for example, carboxyl
groups, carbonyl epoxy and hydroxyl at the base planes and
edges of sheet (Aghigh et al. 2015; Wei et al. 2014; Abraham
et al. 2017). The presence of these oxygen-containing
hydrophilic functional groups can readily extend the oppor-
tunity to tune physicochemical properties of graphene oxide
Environ Chem Lett (2017) 15:643–671
Table 3 Graphene and its
Membrane
applications in varies separation
process Graphene-based membrane
GO membrane
Graphene membrane
GO membrane
GO nanoplatelet membrane
Ozonated GO membrane
GO membrane filters
GO membrane
as well as resultant membrane performance. This abundant
number of polar functionality on graphene oxide offers well
dispersion in aqueous solution without the demand of any
stabilizing agents or surfactants, which enables easy assem-
bly of graphene oxide sheets in aqueous media. The gra-
phene-based materials exhibit facile surface modification
ability through simple chemical reactions, which can be
employed to prepare a series of functionalized graphene-
based membrane materials with excellent separation perfor-
mance (Lai et al. 2016). Moreover, the introduction of the
tunable nanoporous structure into the graphene sheets offers
smooth channels for the transport of water molecules, while
rejecting selective ions substances. The surface physico-
chemical and structural properties were favoring desalination
process by improving water flux, selective sieving and
enhancing antifouling behavior.
Fig. 19 Schematic representation of the preparation of dispersed
graphene oxide nanosheets from graphite. The oxidation of raw
graphite was carried out by treating with an oxidizing agent
comprising of nitric acid and sulfuric acid to form graphite
659
Applications References
Selective ion transport Nair et al. (2012)
Vapor transport Kim et al. (2013)
Selective gas transport Li et al. (2013)
Hydrogen separation Hu and Mi (2013)
Water transport Gao et al. (2014)
Proton exchange Musico et al. (2014)
Bacterial inactivation and removal Nicolaı̈ et al. (2014)
Desalination Lai et al. (2016)
Another significant characteristic feature of graphene
oxide nanosheets is to form tunable stacking pattern under
facile environment. The amorphous distribution of hydro-
xyl, carboxyl and epoxy functionalities inclines to form
structural defects and nanoscale wrinkles in the basal plane
of graphene oxide sheets, which form primary channels for
water permeation across the stacked graphene oxide
nanosheets (Fig. 19). Furthermore, the hydrophobic char-
acter of stacked nanosheet scan forms an almost friction-
less channels which, subsequently, offered low hydraulic
resistance for the permeation water molecules to pass
through the membrane. The molecular transport within
graphene-based membranes is predominantly benefited by
the presence of an abundant number of polar functional
groups bonded to the carbon atoms (You et al. 2016).
These functional groups could able to form a secondary
intercalation. With further exfoliation with water to give dispersed
graphene oxide nanosheets. Reprinted with permission of Abraham
et al. (2017), Copyright 2017, Elsevier
123
660
force of interactions such as hydrogen bond, electrostatic
interaction, dipolar interaction with water molecules to
enhance the permeation properties of graphene and gra-
phene oxide-based membranes. Additionally, oxidized
form of graphene plays the prominent role of spacers that
keep graphene sheets about 0.7–1.0 nm and create almost
frictionless two-dimensional nanochannels of the molecu-
lar transport (Wang et al. 2016).
In particular, methods for preparing graphene can be
categorized into four main classes (a) chemical vapor
deposition of graphene monolayers, (b) crystal growth of
graphene films, (c) mechanical exfoliation of a single sheet
of graphene from bulk graphite and (d) longitudinal cutting
of carbon nanotubes (Perreault et al. 2015; Compton and
Nguyen 2010). The valuable derivatives of graphene such
as graphene oxide and reduced graphene oxide were also
successfully prepared via chemical modification methods.
Scotch tape and chemical vapor deposition techniques have
been extensively used to the synthesis of graphene mono-
layers. The ultrasonic cleavage of graphite and reduction in
graphene derivatives offers the scalable production of
graphene layers (Dreyer et al. 2010).
Transport mechanism
The liquid or water permeation through graphene-based
membrane has attracted considerable attention in spite of
its other potential applications. Liquid transport through
graphene with one-atom thickness is generally accepted,
and even defect-free sheets are primarily impermeable due
to electrostatic repulsive interaction caused by the delo-
calized p-orbital cloud. Therefore, imparting controlled
Fig. 20 Process to create controlled pores in a graphene membrane. Permeability of graphene membrane was enhanced by creating the defects
and pores using different methods. Reproduced with permission from O’Hern et al. (2014). Copyright 2014, American Chemical Society
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Environ Chem Lett (2017) 15:643–671
pores in the graphene sheets by retaining structural integ-
rity exhibits an ultimate thin membrane for desalination
and liquid purification. A number of simulation and
experimental analyses were illustrated that graphene sheets
with artificial pores enhance the permeation and selectivity
(Wang et al. 2017). Figure 20 represents the process to
produce controlled pores in a graphene membrane.
Recently, Sun et al. (2013) illustrated an isotope labeling
method to evidence the mass transport through graphene-
based membranes. They demonstrated by dissolving a
certain amount of deuterium oxide (D2O) as a tracer to
label the source water, the transmembrane diffusion of D2O
through the membrane was determined to prove the
transport of water molecules (Fig. 21). Based on this D2O
labeling technique, they revealed that the water transport
coefficients through the nanochannels of the graphene
oxide membrane are 4–5 orders of magnitude greater
compared to other membranes (Fig. 22) (Sun et al. 2013).
The anomalous water movement through the graphene-
based membrane was caused by low friction flow and
capillary-like driving force restrained between the two-di-
mensional thin-layered channels of the graphene sheets
(Liu et al. 2015; Nair et al. 2012). By pretending that water
molecules inside these nanochannels perform as a classical
liquid, Geim and co-workers make use of Poiseuille’s law
to depict the flow between laminar graphene sheets from
the following equation:
d 4  DP
J¼ ;
12L2  g  h
where ‘L’ the average lateral length of the graphene sheets,
‘h’ the thickness of the graphene membrane, ‘ g’ the
Environ Chem Lett (2017) 15:643–671 661

Fig. 21 a Schematic representation of labeling of 0.1 M MgCl2 solution containing 30 wt% D2O tracers, b D2O diffusion coefficients through
the nanochannels of graphene. Reproduced with permission from Sun et al. (2013). Copyright 2012, American Chemical Society

Fig. 22 Experimental transport measurements through graphene different species depends on the size and charge density. Reproduced
membranes. The transport of molecules through channels of the with permission from O’Hern et al. (2014). Copyright 2014,
graphene-based membranes after the modification. The diffusivity of American Chemical Society

viscosity of water and ‘d’ is the vertical space between
adjacent graphene sheets. The above equitation indicates
that transport of water molecules through the laminates of
graphene sheets showed a flow improved by several hun-
dred factors compared to other classical laminar system. In
general, Hagen–Poiseuille equation is based on the
assumption that no-slip and laminar flow (or molecular
transport with zero velocity) occurs at boundary layer
(Ganesh et al. 2013). The distinctive variation in perme-
ation rate between theoretical calculation and experimental
data illustrated that velocity of fluid across the nanochan-
nels of graphene sheets is not zero (Huang et al. 2013).
From detailed simulation and experimental investiga-
tions, it was evidenced that hydraulic permeation rate

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662
through the nanoporous graphene is prominently reliant on
pore characteristics such as pore size, nature of functionality,
charge density and other physicochemical properties
(Fig. 22). In order to substantiate the effect of pore char-
acteristic on permeation properties, Konatham et al. (2013)
reported that pore size of the nanochanneled graphene-based
membrane has a major influence of free energy profiles and
permeation behavior. It was also demonstrated that transport
or movement of fluid molecules through graphene sheets
significantly correlated with the secondary force of molec-
ular interactions and chemical functionalization at the pores
(Konatham et al. 2013). Furthermore, the presence of charge
density due to polar functionality in the porous channels
function as ionic sieves for higher selectivity and at the same
time offers the easy transport of water molecules. For
instance, the –NH3-functionalized pore failed to cast off the
transport of Cl- ions through the membrane at a moderate
ion concentration due to ion accumulation at the pore
entrance. On the other hand, OH--functionalized pores
contributed encouraging outcomes for the removal of Cl-
ions at both moderate and low ionic strengths specifying
their strong perspective for water desalination.
Goldsmith et al. explore the molecular dynamic investi-
gation to understand the ion transport phenomenon through
0.5 nm pore of the graphene-based membrane. It was wit-
nessed that pore comprising of nitrogen is permissible for
the sodium, potassium and lithium ion, while the pore
terminated by hydrogen permitted bromide and chloride ions
to pass through but did not let fluoride ion. Surprisingly,
smaller ions exhibited lower permeation rates when
Fig. 23 Schematic
representation of a nanoporous
graphene membranes consists of
a single layer of graphene;
b membranes composed of
stacked graphene oxide sheets.
Reproduced by permission of
the Royal Society of Chemistry
2015, Perreault et al. (2015)
123
Environ Chem Lett (2017) 15:643–671
compared to larger ions (Goldsmith and Martens 2010). This
was probably due to the formation of larger hydration sphere
by the smaller ion in the aqueous solution. Therefore,
charged nanochannels in the graphene-based membrane
have the capacity to enhance the membrane performance
including selectivity, permeation rate, lower hydraulic
resistance, higher chemical stability and mechanical
strength. The molecular transport through the different type
of graphene-based membrane is presented in Fig. 23. Tanugi
and Grossman have carried out the detailed investigation of
the effect of pore chemistry by using passivated hydrogen
atoms and hydroxyl groups for the desalination of graphene-
based membranes. They observed that the hydrogen-termi-
nated nanopores exhibited low ion selectivity, whereas
hydroxyl group-functionalized pores showed improved
hydraulic permeation rate (Cohen-Tanugi and Grossman
2012). This behavior was due to the affinity of polar func-
tional groups such as hydroxyl group and a carbonyl group;
the acid group can easily interact with the water molecules
and allow to pass through the nanochannels of the graphene-
based membrane. In order to substantiate this, simulation
study was carried out; the result revealed that the water
permeation through the membrane was up to 66 L/cm2/day/
MPa with salt rejection capacity of 99%. However, flux
rate through the conventional reverse osmosis membrane
reached approximately 0.01–0.05 L/cm2/day/MPa with
similar salt rejection (Daer et al. 2015). These experimental
results demonstrated the enormous possibility for deploy-
ment of functionalized nanoporous graphene-based mem-
branes as potential desalination applications.
Environ Chem Lett (2017) 15:643–671
Functionalization of graphene family
nanomaterials
The modification of graphene sheets with various active
functional groups as well as the integration with other
classes of inorganic nanoparticles allows significant chan-
ges in surface and physicochemical properties of the
resultant surface. The functionalized graphene offers new
class of engineered materials with exciting opportunities in
desalination and other several specific applications. The
chemical modification or surface functionality of these
graphene-based materials offers significant changes in
physicochemical properties and allowed for a wide range
of material science strategies to improve the permeation
and selectivity of the resultant membrane (Liu et al. 2015;
You et al. 2016; Chang and Wu 2013). In recent years,
several efforts have been put forward in the synthesis,
chemical modification and surface functionalization gra-
phene sheet with hydroxyl-, amine- and carboxylate-ter-
minated groups for the enhancement of desalination
performance. Generally, surface modification can be rela-
ted to the formation of new sp3-hybridized carbon atoms
from the sp2-hybridized carbon network by simultaneous
loss of electronic conjugation (Cheng et al. 2016). The
membrane of graphene was designed in such a way that it
could serve as ionic sieves and precisely arranged func-
tional groups can efficiently guide the water molecules to
pass through it. As demonstrated in Fig. 24, the graphene
monolayers can easily be functionalized by several modi-
fication methods to facilitate the physicochemical behavior
and surface properties.
Fig. 24 Schematic representation of a chemical modification of
graphene-based materials. To enhance the versatility and applicability
of graphene-based materials, various chemical modifications can be
663
The covalent and non-covalent interaction is one of the
most regularly employed methods to prepare functional-
ized graphene materials. The non-covalent interactions
between graphene organic species endorse the binding of
organic functionality on graphene surfaces. The organic
species such as polymers, surfactants and the surface-
modifying agent can easily interact with graphene sheets
by means of electrostatic interaction, p–p stacking,
hydrophobic interaction or dipolar interaction to modify
the graphene properties (Ali et al. 2016). Ali et al. (2016)
reported the covalent interaction of active silane-termi-
nated oligothiophene functionality with to graphene oxide
sheets. The benefit of this reaction is that the covalent
bond formation can be easily completed within a fraction
of minutes by using microwave radiation (Ali et al. 2016).
In addition to this, graphene or graphene oxide can be
modified with porphyrins via amide bond formation
between carboxylic groups of graphene oxide and amine-
functionalized porphyrins as shown in Fig. 25. The
amine-functionalized polyethylene glycol can also be
easily attached to graphene oxide via amide bond for-
mation. The advantage of polyethylene glycol-modified
graphene oxide is well dispersion in the aqueous medium
and other common organic solvents. Moreover, it enhan-
ces the hydrophilicity of resultant graphene and offers
easy transport of water molecules through graphene-based
membranes. Georgakilas et al. (2012) illustrated the
reaction of graphene oxide with polyallylamine (AAA). In
this reaction, numerous epoxy groups of graphene oxide
react successfully with amine groups of PAA and form the
effective cross-linking between graphene oxide sheets
carried out with tailor-made properties. Reproduced by permission of
the Royal Society of Chemistry 2013, Chang and Wu (2013), Ali et al.
(2016)
123
664
Fig. 25 Surface functionalization of membranes with graphene
nanomaterials. The chemical modifications of graphene oxide with
various functional groups to enhance the membrane physicochemical
(Georgakilas et al. 2012). Cohen-Tanugi and Grossman
(2012) examined the effect of functionality on physico-
chemical and permeation properties of nanoporous gra-
phene-based membranes. They stated that the pore
comprising of polar functional groups exhibited higher
permeation flux with significant improvement in the ion
selectivity (Cohen-Tanugi and Grossman 2012). Further-
more, the presence of these functional groups such as
hydroxyl, carbonyl and acid groups in the pores of
membrane facilitates the transport of water molecules by
suppressing ion passage.
The modification of graphene oxide can also be carried
out by grafting with polyvinyl alcohol via ester bonds
between the carboxylic groups of graphene oxide and the
hydroxyl groups of polyvinyl alcohol. These covalent
bonds can be formed either directly or after the conver-
sion of carboxylates to acyl chlorides. The polyvinyl
alcohol-functionalized graphene oxide composite is
highly dispersible in hot water and other common polar
organic solvents such as dimethyl sulfoxide, dimethyl-
formamide, dimethylacetamide and N-methyl-2-pyrroli-
done. Lin et al. (2011) reported an effective way to
prepare the polyethylene chains grafted to the surface of
graphene oxide, which gives rise to a high polymer
grafting efficacy and increases crystallization temperature
of 10 °C compared with the pristine polymer (Lin et al.
2011). Lee et al. (2010) described an effective atom
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Environ Chem Lett (2017) 15:643–671
properties and performance. Reproduced with permission from
Perreault et al. (2014). Copyright 2013, American Chemical Society
transfer radical polymerization technique to modify gra-
phene sheets with highly functional polymers. In this
technique, polar polymer chains were directly developed
over the surface of graphene oxide through living radical
polymerization. The resultant nanocomposites exhibited
improved thermal stability, chemical resistance and
mechanical strength. The facile hydrophilic modification
of graphene oxide with this method offers favorable
properties to forms an effective membrane material for
the desalination application (Lee et al. 2010). Recently,
modification of graphene oxide with imidazolium
derivatives has been described by Karousis et al. (2011).
In this method, 1-(3-aminopropyl)-imidazole was cova-
lently attached through carboxylic groups of graphene
oxide via amide bond formation. Subsequently, the hete-
rocyclic ring was transformed through N-methylation to
its ionic imidazolium analog. Ramanathan et al. (2008)
reported the effective modification of graphene oxide
sheets comprising of reactive functional groups via
polymethyl methacrylate functionalization. The resulting
nanocomposites were highly dispersible in common
organic solvents and employed as reinforcement fillers in
the preparation of polymethyl methacrylate composite
films. Georgakilas et al. (2012) reported the modification
of graphene by treatment with exfoliated graphene
sheets concentrated HNO3, which introduces hydrophilic
functional groups (–COOH, –C=O, –OH). After
Environ Chem Lett (2017) 15:643–671
functionalization, membrane exhibited better desalination
ability with higher hydraulic permeation and ion selec-
tivity (Georgakilas et al. 2012).
Desalination application of graphene-based
membranes
It is extremely stimulating to understand the effectiveness
of new graphene-based membrane for the field of desali-
nation by uplifting performance compared to contempo-
rary desalination technologies. Moreover, membrane-
based desalination process is the significant alternative
because of its inherent characteristic features such as
being energy efficient, without any phase change, opera-
tionally intensive and hence affordable at a commercial
scale (Ganesh et al. 2013; Georgakilas et al. 2012). For
this purpose, Safarpour et al. (2016) fabricated the gra-
phene oxide/TiO2 composite nanofiltration membrane
with an average pore diameter of 3.5 nm by incorporating
TiO2 nanoparticles between graphene oxide nanosheets to
expand the gaps between the nanochannels. The hybrid
nanofiber graphene oxide/TiO2 membrane has attained
100% rejection of the detrimental reactive dyes such as
methyl orange and rhodamine B from the aqueous stream.
Daer et al. (2015) described the molecular dynamics
simulation for the freestanding graphene oxide mem-
branes. They stated that graphene oxide membrane is the
excellent candidate for efficient desalination applications
compared to other polymer-based reverse osmosis mem-
branes. The freestanding graphene oxide membranes have
the capacity to reject salt by 100%, while instantaneously
permitting outstanding hydraulic permeation, with double
the permeation ability of current reverse osmosis tech-
niques, since the graphene oxide membranes are in
ultrathin thickness. Feng et al. (2016) demonstrated the
preparation of graphene oxide framework membrane via
selective cross-linking with 1,4-phenylene diisocyanate
for seawater desalination. They stated that the presence of
three-dimensional structure exhibits reduced resistance of
mass transfer through graphene oxide framework mem-
brane, thereby significantly enhancing the water perme-
ation rate. For an 18 lm thickness of graphene oxide
framework membrane at 90 °C, the water flux is
11.4 kg m-2 h-1 and ion rejection is over 99.9% for
desalination of 3.5 weight percent seawater.
Recently, Kafiah et al. (2016) reported the fabrication
of nanoporous graphene-based membrane with the very
less defective structure for desalination application. For
this purpose, chemical vapor deposition method has been
employed to prepare the monolayer graphene sheets. The
effect of this monolayer graphene on membrane
665
performance was studied by using two commercial
microfiltration membranes, namely polyvinylidene diflu-
oride and polypropylene. The permeation properties of
resulting membranes were examined by movement of an
electrolyte such as potassium chloride ions exploiting a
side-by-side diffusion. The presence of less defective
monolayer graphene increased the rejection of ions up to
84% compared to pristine polymer membrane. Ali et al.
(2016) investigated the applicability of thin-film
nanocomposite membranes after the inclusion of graphene
oxide for efficient desalination application. From the
experimental evidence, it was stated that inclusion of the
small amount of graphene oxide into the polymer mem-
brane matrix effectively increases the mechanical
strength, chemical resistance, thermal stability, hydraulic
permeation rate, fouling and chlorine resistances proper-
ties of the resultant membrane. At 15 bar transmembrane
pressure, a water permeation rate of 29.6 L/m2 h and a salt
rejection capacity of C97% were achieved for a saline
water contains 2000 ppm of NaCl. Moreover, the pre-
pared membrane showed significant resistance toward
both acidic and alkaline solutions (Fig. 26). Xu et al.
(2016) illustrate the preparation of highly stable graphene
oxide membrane on polydopamine-functionalized mem-
brane for seawater desalination process. For desalination
of 3.5 wt% seawater at 90 °C, high water fluxes of
48.4 kg m-2 h-1 and high ion rejections of over 99.7%
can be reached for the graphene oxide membrane, which
is much higher than those achieved from conventional
porous inorganic membranes.
Lai et al. (2016) prepared thin-film composite mem-
brane by the inclusion of graphene oxide with a different
additive dosage ranging from 0 to 0.5 wt% into microp-
orous polysulfone substrate. The resultant thin-film
nanocomposite membrane of 0.3 wt% graphene oxide
showed the maximum water flux with a rejection rate of
Na2SO4, MgSO4, MgCl2 and NaCl obtained at 95.2, 91.1,
62.1 and 59.5%, respectively (Lai et al. 2016). The mixed
matrix membrane with polyamine-functionalized graphene
oxide exhibited superior hydrophilicity, hydrodynamic
permeation and antifouling properties over a prolonged
period of time. Polysulfone membranes containing 1 wt%
ethylenediamine-functionalized graphene oxide and 5 wt%
polyethylene glycol-600 additives displayed remarkably
high-pure water flux of 170.5 L/m2 h, a three fold increase
over corresponding control membrane (Zambare et al.
2017). Nan et al. (2016) reported the preparation of posi-
tively charged nanofiltration membrane through via poly-
ethyleneimine and the layer-by-layer assembly of graphene
oxide for effective desalination. The unique 2D structure
and high aspect ratio of graphene oxide nanosheets facili-
tated them to easy alignments of the membrane surface.
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666
Fig. 26 Salt rejection and water flux of thin-film composite and thin-
film composite/graphene oxide membranes at different feed solution
pH. Describes the presence of graphene oxide in thin-film
The inherent low hydraulic resistace of nanopores within
the graphene oxide membranes gives rise to a high water
permeation rate. The modified membrane achieved a water
permeation rate of 4.2 L/m2 h bar at 30 °C and salt
rejections of 93.9 and 38.1% for Mg2? and Na? ions.
Safarpour et al. (2015) reported the preparation of mixed
matrix polyvinylidene difluoride membrane comprising of
reduced graphene oxide)/TiO2 nanocomposite. The modi-
fied membranes showed better water permeability and
fouling resistance properties compared to the pristine
polyvinylidene fluoride. When the content of reduced
graphene oxide/TiO2 was 0.15 wt%, the water flux reached
a maximum value of 45.0 kg/m2 h, which is nearly twice
of that of the bare polyvinylidene fluoride membrane, i.e.,
23.1 kg/m2 h. Bano et al. (2015) reported the graphene
oxide blended polymer matrix for desalination application.
They have illustrated that the presence of graphene oxide in
polyamide nanofiltration membrane exhibited higher
hydraulic permeation rate, ion selectivity and excellent
antifouling nature during the desalination. The graphene
oxide–polyamide membrane (0.2 wt% membrane) was
found to be 12-fold better than with either of the pristine
polyamide or graphene oxide membrane. The overview of
graphene-based membranes for desalination is presented in
Table 4.
Challenges for graphene-based membrane
As an excellent membrane material for desalination, gra-
phene and its derivatives offer a tremendous advantage
over existing other materials such as zeolite, TiO2 and
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Environ Chem Lett (2017) 15:643–671
nanocomposite membrane on the water flux and salt rejection
behavior. Reprinted with permission of Ali et al. (2016), Copyright
2016, Elsevier
other nanomaterials. Late advances in these materials
guarantees as a standout among the most dependable
answers for lower the energy utilization to empower more
reasonable improvement of desalination technology (Liu
et al. 2015; Perreault et al. 2015). However, several critical
problems still remain open. According to Abraham et al.
(2017), one of the foremost disadvantages for graphene-
based materials is to regulate their inherent structural and
physicochemical properties such as purity, the size of the
sheet, propensity to agglomeration, the length of the sheets
and number of layers for graphene, etc. In addition to this,
it is difficult to provide the reproducible approaches to
control a number of layers and oxidation level of graphene
sheets (Cohen-Tanugi and Grossman 2012). The simula-
tion and experimental desalination data illustrated that the
hydraulic resistance and selective transport properties are
majorly governed by the favorable porous structure and
physicochemical properties. This serves as a stimulant for
the incessant investigation of graphene-based materials for
effective desalination application. However, it is impera-
tive to tolerate in mind that the intact non-functionalized
graphene sheets will always remain as a computational
fantasy. In reality, the existence of ideal one-atom thick-
ness graphene sheet is almost impossible due to the
uncertainties and inconsistency of the production (Perreault
et al. 2014; Miculescu et al. 2016).
Even though much considerations have been engrossed
on the possible advances of graphene-based membrane
materials for desalination process, there is also an essential
research needs to be carried out to identify the effect on
potential human health and environmental risks. In spite of
the several potentials and advances they have presented, on
Environ Chem Lett (2017) 15:643–671 667

Table 4 Overview of graphene-based membranes for desalination

Membrane Method Type Flux Contact Applied Rejection % References
angle (°) pressure

GO/PSF Phase inversion UF 450 L/m2/h 82.5 100 kPa BSA 99% Bano et al. (2015)
2
GO/PVDF Phase inversion UF 26.4 L/m h 60.5 100 kPa BSA 79% Hung et al. (2014)
GO/PSF Phase inversion NF 50 L/m2 h 53 400 kPa Na2SO4 72% Zhao et al. (2013)
GOf/PSF Phase inversion UF 135 kg/m2 h 74 100 kPa BSA 95% Ganesh et al. (2013)
GO/PSF Phase inversion UF 153.5 L/m2 h 63.1 100 kPa PEG 85% Zhao et al. (2013)
GO/PECs Self-assembly NF 7.1 kg/m2 h 500 kPa Mg2? 92.6% Yu et al. (2013)
GO/MW CARBON Phase inversion UF 410 L/m2 h 52.5 100 kPa – Wang et al. (2012)
NANOTUBE/PVDF
GO/PES Phase inversion NF 53 kg/m2 h – 400 kPa Dye 96% Zhang et al. (2013)
GO/PVDF Phase inversion UF 401.3 L/m2 h 51 100 kPa BSA 57% Zinadini et al. (2014)
2
GO/PVDF Phase inversion MF 324.5 L/m h 60.5 25 kPa Yeast 80% Xu et al. (2014)
GO/PES Self-assembly RO 28 L/m2 h 55.4 5500 kPa NaCl 98% Zhao et al. (2014)
GO/PA Self-assembly RO 14 L/m2 h – 1550 kPa NaCl 96.4% Kim et al. (2013)
GO/PAN Self-assembly NF 4137 g/m2 h – 5 kg/cm2 – Choi et al. (2013)
GO/PA Covalently bonded RO 41.4 L/m2 h 47 2760 kPa NaCl 97.8% Dikin et al. (2007)

the other hand, graphene might also result in drastic
environment and safety impact. Due to the increasing
extensive usage and a wide spectrum of applications, gra-
phene may release quickly to the environment. Spread of
hazardous and detrimental graphene-based materials into
the environment is another major concern at this point
(Cruz-Silva et al. 2016). From the experimental investi-
gation, the toxic effect of graphene-based engineered
materials has been proved in recent years with the help of
model organisms. Furthermore, it was also observed the
strong affinity of graphene and its derivatives toward the
hazardous heavy metal ions from aqueous solution (Müller
2013). As a result, the hazardous effects of graphene-based
materials on environmental threat should be effectively
evaluated, as a precautionary measure for the sustainable
development of graphene-based membrane for desalination
application.
Conclusion and future perspective
Over the last decade, there have been considerable
advances in the applications of carbon nanotube- and gra-
phene-based membranes in the areas of desalination,
wastewater treatment and environmental remediation. The
effective application of these materials in the fabrication of
vertically aligned nanocomposite membranes has allowed
the exploration of a new-generation technology for the
desalination. The positive transformation of these mem-
branes offers excellent potential to understand the sus-
tainable development of contemporary desalination
technologies. The exploration of carbon nanotubes,
graphene and its derivatives can easily be modified via
chemical treatment to enhance the hydrodynamic perme-
ation and ion selectivity of desalination resultant mem-
brane. However, large-scale production of carbon
nanotube- and graphene-based membrane for desalination
technology requires extensive investigation on synthesis
and optimization of fabrication methods. Moreover,
detailed simulation and experimental analysis is essential
for the sustainable implementation of desalination tech-
nology by considering social, environment and economic
point of view. For this purpose, the scientists and engineers
expand the key research areas that comprise of wide
spectrum of multidisciplinary research goals. By looking
closer to performance chart for functionalized carbon
nanotube- and graphene-based membranes versus existing
technologies, it clearly shows the predominant advance-
ment of these materials over existing other membranes for
desalination process.
The detailed exploration is necessary for the holistic
development of highly selective and efficient desalination
technology. The verbalization of combined research and
development offers effective transfer of research results
into sustainable innovations. There is a positive industrial
approach toward the recognition of environmentally
friendly processes and products. The exploitation and dis-
semination of health and environmental safety of carbon
nanotube- and graphene-based membrane desalination
process, entire life cycles and establishment of long-term
roadmap deliver a cohesive structure for moving toward
sustainable technology. However, the substantial effort is
still necessary to fill the gaps and diminish disparities
between the reality and pipe dream, with the accelerating

123
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knowledge and technological transfer from academic to
industries.
Acknowledgements The authors thank the Director, NITK Sur-
athkal, India, for providing the research facilities. The authors also
thank Vision Group on Science & Technology, Department of I.T,
B.T, Government of Karnataka, for the CESEM award.
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