Desalination 437 (2018) 59–72

Contents lists available at ScienceDirect

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

A review of graphene-based separation membrane: Materials, T

characteristics, preparation and applications
⁎ ⁎⁎
Na Songa,b, Xueli Gaoa,b, , Zhun Mac, , Xiaojuan Wanga,b, Yi Weia,b, Congjie Gaoa,b
a
Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, Qingdao 266100, China
b
College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China
c
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China

G RA P H I C A L AB S T R A C T

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

Keywords: Membrane desalination has become an important solution to global water problems. Graphene-based materials
Graphene-based separation membrane have excellent advantages in the desalination process due to their intriguing features, including single atomic
Pressure-driven membrane layer structure, large specific surface area, hydrophobic property, rich modification approaches, etc. After an
Concentration-driven membrane introduction of membrane, graphene and graphene oxide (GO), this review systematically summarizes the
Electric-driven membrane
current progress and gives an insight into the graphene-based separation membranes (GBSMs). The applications
of the pressure-driven graphene-based membranes are introduced and their performances are listed and ana-
lyzed. By molecular dynamics simulation (MDS), the researchers predict the excellent performances of GBSMs,
including high water flux, good salt rejection, etc. which have been verified in subsequent experiments. We
believe that the application of graphene-based materials in pressure-driven membrane is worthy of further ex-
ploration. Several researchers have prepared electric-driven membranes with graphene-based materials, since
their good stabilities and water-retention. However, graphene is not efficient in forward osmosis membrane area
for now. In spite of the shortcomings like weak mechanical strength of single layer graphene, difficult to prepare
nanopores on graphene film and hard to integrate with polymer, we hold the opinion that graphene-based films
still have great research value especially in the membrane separation technology.

1. Introduction considering the distribution of water on the planet. Approximately 98%

of our water is salty and only 2% is fresh. Of that 2%, almost 70% is
Understanding the problem of fresh water scarcity begins by snow and ice, 30% is groundwater, less than 0.5% is sur [1].

⁎
Correspondence to: X. Gao, Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, Qingdao 266100, China.
⁎⁎
Co-corresponding author.
E-mail addresses: gxl_ouc@126.com (X. Gao), zhunma201007@gmail.com (Z. Ma).

https://doi.org/10.1016/j.desal.2018.02.024
Received 23 May 2017; Received in revised form 9 February 2018; Accepted 22 February 2018
Available online 07 March 2018
0011-9164/ © 2018 Published by Elsevier B.V.
N. Song et al.
Desalination is the technology and process by removing most of the salt
from saline water to get pure water which achieve the life and pro-
duction water standard. As a kind of technology which can increase the
amount of freshwater, desalination has become a strategic choice to
solve the crisis of water resources. Currently, the global volume of
desalinated water has exceeded 80 million m3/day, alleviating water
shortages which have affected over 200 million people [2]. This con-
siderable volume of water was obtained by one of two main desalina-
tion processes. One technique extracts the water using reverse osmosis
(RO), distillation, freezing, hydration and solvent extraction etc., while
the other technique extracts the various salts from saline water using
such methods as ion exchange, electrodialysis (ED), adsorption capa-
citance, pressure impregnation and forward osmosis (FO) technology.
In 1953, Charles E. Reid invented RO in the United States and this
process has led to the innovation of water filter appliances, which in
recent years have become a most highly sought-after domestic com-
modity. The extent of membrane usage has substantially increased each
year. The development of nanotechnology and nanomaterials provides
an opportunity to improve the structure and properties of water-
permeable membranes. Carbon nanotubes (CNTs), water channel pro-
teins, molecular sieves and metal organic framework compounds
(MOFs) have made a significant impact on the RO membrane permea-
tion flux. In particular, the recent advent of graphene nanochannels for
rapid water flow has focused attention on the area of desalination
membrane preparation. This review focuses on the graphene and its
composite membranes' synthesis methods, properties and application.
Fig. 1 is Summary of applications, different classifications of graphene-
based separation membranes (GBSMs).
2. Backgrounds of membrane and graphene for separation
2.1. Basic knowledge for separation membrane
With the development of science and technology, membranes have
been more prevalent in scientific research, production and engineering.
A membrane is seemingly only a thin barrier but it has extraordinary
influence and increasing widespread application. A variety of new
membrane materials, devices, processes and application technology
continue to emerge. In recent years, membrane technologies have de-
veloped in rapid succession; these include microfiltration (MF),
Fig. 1. Summary of applications, different classifications of GBSMs.
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Desalination 437 (2018) 59–72
ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO), forward
osmosis (FO), dialysis, electrodialysis (ED), gas separation and perva-
poration. The application of these procedures has produced great eco-
nomic and social benefits, and has become one of the most important
means of separation science.
A separation membrane can be described as a semi-permeable
barrier between two phases that allow certain molecules to pass
through. The barrier can be solid, liquid, or even gas, and its semi-
permeable property is mainly to ensure separation. Membranes retain
molecules according to a variety of different characteristics such as the
molecular diameter, the permeability coefficient, charge and the solu-
bility level. Table 1 shows the basic concept of several major membrane
separation processes and characteristics.
In recent years, the concept of nanotechnology has been used in film
technology and this organic combination has achieved satisfactory re-
sults [3]. By adding nano-functional materials to conventional mem-
brane materials, it is possible to construct, modify and optimize the
membrane passages to ultimately give the film a good permeability,
desalination and antifouling performance. Many nanomaterials have
excellent performance in the field of membrane modification tech-
nology, such as nano-silica (SiO2), metal organic framework com-
pounds, carbon nanotubes, aquaporins, zeolites, graphene and so on.
Nano-zeolite has a large specific surface area, stable hydrothermal
performance and rich micropores, therefore it has great potential for
enhancing membrane material. In 2015, Dong et al. [4] doped nano-
zeolite into the polysulfone membrane with in-situ blending to improve
the membrane's hydrophilicity and inhibit the growth and reproduction
of micro-floras, which have a bacteriostatic effect. Carbon nanotubes as
a one-dimensional carbon material with a similar tubular structure, are
expected to build the membrane channels which allow water molecules
to pass quickly, prompting a substantial increase in membrane perme-
ability. Esfahani et al. [5] investigated the properties of PSf ultra-
filtration membranes doped with nano-TiO2 and SWCNTs. The results
revealed that the membrane properties fluctuate according to the extent
of nanoparticle doping. When the ratio of nano-TiO2 and SWCNTs is 1:1
(total 1 wt%), the prepared mixed matrix membrane has the best per-
meability, the highest rejection rate of humic acid and proficient anti-
fouling ability. In 2016, Xu et al. [6] blended MIL-101 (Cr) into ultra-
thin composite membranes. The composite membrane's water flux was
1.58 times higher than that of the unmodified membrane. The perfor-
mance of the membrane can be controlled by adjusting the doping
amount of the MIL-101 (Cr) in the membrane to achieve different se-
paration requirements. The aquaporin is composed of a similar hour-
glass structure with the narrowest part not exceeding 2.8 Å. It can allow
water molecules to pass through rather than salt ions. Wang et al. [7]
used a self-assembly method to prepare a new aqua protein biomimetic
membrane. At 0.2 MPa, the water flux can reach 22 L/m2·h, and the
retention rate of NaCl and MgCl2 is approximately 75% and 97%, re-
spectively. The membrane has good permeability while maintaining a
high desalination rate. Nano-silica is an inorganic chemical material
with a narrow particle size distribution and a large specific surface area.
Incorporating it into the membrane can improve the material's aging
and chemical resistance. Kebria et al. [8] prepared an ultra-thin com-
posite nanofiltration membrane by adding nano-silica to the aqueous
solution interface. The water flux was 13.3 L/m2·h, but the removal rate
of crystal violet was slightly lower. Current researchers were concerned
about the nano-materials in membrane materials, although there were
no unexpected results, there is still more scope for development. Re-
cently, Zhang et al. [9] published an article about graphene for capa-
citive deionization and stated that graphene is one of the most pro-
mising capacitive desalination materials. It is known to have strong salt
removal abilities due to its high theoretical specific surface area, good
electrical conductivity and controllable morphological structure.
N. Song et al. Desalination 437 (2018) 59–72

Table 1
The basic concept of several major membrane separation processes and characteristics.

Process Concept Function Driving force Pass materials Intercepted materials

MF Porous membrane, remove micro- Pressure driven Water, solvent, Suspended solids, bacteria, micro-
particles from solution solute particles

UF Remove colloid from solution, all Pressure driven Solvent, ions, micro- Protein, enzyme, bacteria, viruses,
macromolecules molecule latex, micro-particles

NF Remove salts and low molecular Pressure driven Water, solvent Inorganic salts, sugars, amino acids,
substances from solution BOD, COD. etc.

RO Remove salts and low molecular Pressure driven Water, solvent Inorganic salts, sugars, amino acids,
substances from solution BOD, COD. etc.

FO Remove salts and low molecular Concentration driven Water, solvent Inorganic salts, sugars, amino acids,
substances from solution BOD, COD. etc.

Dialysis Remove salts and low molecular Concentration driven Ion, low molecular, Urea, uric acid, inorganic salt,
substances from solution acid, alkali sugars, amino acids

ED Remove ions from solution Potential difference Ions Inorganic ions, organic ions
(PD)

Abbreviations: BOD, biochemical oxygen demand; COD, chemical oxygen demand.

2.2. Basic knowledge for graphene 2.2.2. One-atom thickness

Graphene is a single layer of carbon with a honeycomb structure
made up of sp2 hybridization carbon atoms which are linked together
with strong sigma keys. It exhibits many unique properties including a
highly specific surface area, superior thermal conductivity, remarkable
elasticity and strength, as well as excellent charge carrier mobility [10].
Due to these valuable properties, graphene has remained at the core of
scientific research since its advent, with many of its successful accom-
plishments being transformed into practical applications. In addition,
the derivatives of graphene extend its practicability by combining with
a variety of functional composite materials. Graphene and graphene
derivatives are often used in fuel cells [11,12], supercapacitor [13,14],
capacitive deionization [15–17], desalination [18–20] and so on. Ac-
cording to previous reports, graphene derivatives can amalgamate with
the following materials: inorganic nanostructures, organic crystal,
polymers, organic framework, biological materials and carbon nano-
tubes. Membrane separation technology requires membranes with high
strength, non-toxic smooth surfaces, channels and the ability to trap
other substances. Graphene and its composite materials perfectly satisfy
these basic demands.
2.2.1. Mechanical properties
Atomic force microscopy (AFM) measures the performance of free-
standing monolayer graphene membrane based on nanoindentations
[21]. With a breaking strength of 42 N·m−1 and a Young's modulus of
TPa 1.0, graphene is an extremely strong material. Yet, an external
mechanical load can change the electronic properties of graphene
thereby affecting its field emission performance [22,23]. Graphene's
ability to absorb pressure can also be affected by different degrees of
axial compression [24]. The varying sizes of buckling stress and strain
are measured using a cantilever beam. When graphene is used as a
membrane material, it can provide a stronger support force and ad-
justable sheet spacing. Therefore, the mechanical strength and con-
trollability of the membrane can be augmented.
After analysing the various attributes of graphene and its applica-
tion with membranes, it can be concluded that the initial access method
is simple and direct. Konstantin et al. [25], graphene's discoverer, found
that the cellophane tape which his students used to remove dirt from
objects, removed dozens of atomic layers from a piece of graphite. He
then repeatedly applied and removed the cellophane tape on the gra-
phite, thereby obtaining a one atom thick piece of graphene material
(0.335 nm). Surwade et al. [26] uses a single layer of graphene as a
separation membrane to desalinate seawater. He examined the trans-
port of ions and water through a suspended monolayer graphene
membrane which has a stable nanoscale pore and is produced by
oxygen plasma etching. Thus, they validated the effectiveness of gra-
phene-based desalination. Fig. 2 is a characterization of nanoporous
graphene. These membranes exhibit both high water penetrability and
salt rejection properties.
2.2.3. Specific surface area (SSA)
To date, the reported [27] SSA values of carbon materials derived
from GO have been well below 2630 m2/g, and the specific surface area
of common active carbon is only 1500 m2/g. Zhang et al. [28–30]
prepared graphene/carbon nanotube composites using a modified ex-
foliation approach. The excellent desalination yield of the graphene/
carbon nanotube composite electrodes is attributed to its high con-
ductivity and large accessible surface area, which are crucial for the CDI
performance. This property ensures that graphene can adsorb a variety
of materials and has the capacity to become an energy storage material.
In the field of desalting, the large specific surface area of graphene
membrane is more suitable for desalination than that of other mem-
brane materials. Zhu et al. [31] doped GO functionalized with zwit-
terionic into the membrane, utilizing the characteristic of a large spe-
cific surface area, and obtained a new loose nanofiltration membrane.
Fig. 3 is the preparation process of functionalized graphene nanosheets
(a) and G-PANCMI (graphene‑poly acrylonitrile‑co‑maleimide) compo-
sites (b). These novel nanofiltration membranes have high salt perme-
ability and high rejection rates for low molecular dyes, as well as

61
N. Song et al.
Fig. 2. Characterization of nanoporous graphene [26].
improved mechanical strength. This shows that the novel nanofiltration
membrane has the potential to separate organic dyes and salts from
textile wastewater. Wang et al. [32] developed a new method to fab-
ricate graphene composite membrane by attaching the amine and car-
boxylated graphene to a polymer matrix (G-PANCMI) to obtain an ul-
trafiltration membrane for the application of the actual downstream.
Fig. 3. The preparation process of functionalized graphene nanosheets (a) and G- PANCMI (graphene‑poly(acrylonitrile‑co‑maleimide) composites (b) [18].
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Desalination 437 (2018) 59–72
The results show that the modified supported graphene membrane has
excellent hydrophilicity (water contact angle is reduced to zero). It is
worth mentioning that minor selectivity alterations can be observed
with increasing membrane permeability.
2.2.4. Hydrophobic property
There is much research to suggest that graphene is hydrophobic.
Although GO is a non-stoichiometric material, many oxygen-containing
functional groups are present at both the plane and the edge, and a
large amount can be removed by chemical reduction. Leenaerts et al.
[33] stated graphene is hydrophobic using density functional theory.
The binding energy between water molecules is stronger than droplets
and graphene, so the water droplets tend to absorb more water mole-
cules instead of graphene. This phenomenon illustrates that graphene is
hydrophobic. Wang et al. [34] prepared graphite oxide by oxidising
natural graphite and then obtained graphene by hydrazine hydrate
reduction. The contact angle of water drops on the surface is 67.4°.
Consequently, the results confirm that GO is hydrophilic. Liu et al.,
2011 [35] identified that the superposition of irregular multilayer
graphene nanofragments formed the micro structure while graphene
nanodebris folding together formed the nanostructure. The existence of
the micro and nanostructure on the graphene surface enhanced the
hydrophobic properties. The hydrophobic graphene desalination
membrane reduces the frictional force between the membrane and the
water molecules. In this manner, the water molecules can easily pass
between the graphene sheets, and the water flux is increased. In addi-
tion, this characteristic can reduce the film contamination rate because
the particles are not easily attached to the membrane surface.
2.2.5. Rich modification approaches
Due to the stability of the two-dimensional structure, graphene is
N. Song et al.
Fig. 4. Schematic illustration of the reduction process, including photographs of (a) the graphite oxide aqueous solution and (b) the stably dispersed graphene aqueous dispersion [39].
relatively unreactive with other substances. Therefore, researchers de-
veloped the Hummers method to prepare GO which is the precursor of
graphene. It has a hydrophilic surface and can hydrogen bond as well as
form epoxy group and carbonyl functional groups with other elements
(as shown in Fig. 4). This method strengthens the adsorption ability,
water-solubility and other properties. Zhang et al. [36] designed a
novel, ion-selective 3D graphene electrode and originally prepared to
overcome the co-ions expulsion effect and improve the desalination
performance in the capacitive deionization process. The electrodes
were fabricated by grafting sulfonic and amine functional groups on
three-dimensional graphene (3DGR) using an aryl diazonium salt so-
lution and 3‑aminopropyltriethoxysilane, respectively. These grafted
groups can act as ion-selective functional coatings, which can minimize
the co-ions expulsion effect and increase the charge efficiency. Our
laboratory is currently studying the surface of the GO film implanted
with negatively charged carboxyls, to achieve the role of the exclusion
of negatively charged particles, as a potential nanofiltration membrane
[37]. It can improve the salt rejection capability and has the potential to
become a nanofiltration membrane.
In addition to the chemical modification of the graphene surface,
the physical surface modification is an area of research interest.
Chemical methods will inevitably break some valence bonds on the
surface of the graphene. Fortunately, the modification method can keep
the surface of graphene complete and retain the electrical properties of
graphene, such as high mobility and high electrical conductivity. This
modification can further regulate graphene function. Zhang et al. [38]
modified a 2 nm layer of lead sulphide quantum dots by using the
method of electron beam evaporation on a graphene surface. Lead
sulphide modification of graphene can be used as a light sensor because
lead sulphide quantum dots is suitable for a quantum confined effect as
its absorption spectrum extends to the visible light and near infrared
region.
2.2.6. Other properties
Apart from the aforementioned properties, graphene has many
other characteristics such as the quantum Hall effect (QHE), carrier
mobility at room temperature (~10,000 cm2·V−1·s−1), good optical
transparency (~97.7%), excellent electric conductivity
(3000–5000 W·m−1·K−1) [40], and highly negatively charged GO. Lai
et al. [41] prepared thin nanocomposite filtration membrane with
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Desalination 437 (2018) 59–72
highly negatively charged GO for enhancing salt removal performance.
The salt's rejection of the TFN film with 0.3 wt% GO was the highest.
The presence of Na2SO4, MgSO4, MgCl2 and NaCl was 95.2%, 91.1%,
62.1% and 59.5%, respectively.
In current membrane technology, membrane separation is the
fastest growing and most widely used procedure. Composite films
doped with nano-particles are used to improve the performance of
predominantly, pressure-driven membranes. Therefore, this paper fo-
cuses on the summary and prospect of the graphene-based pressure-
driven membranes.
3. Synthetic methods
3.1. Preparation of graphene and graphene oxide
The high yield and inexpensive preparation technology of graphene
is the fundamental basis of its widespread application. Many scholars
have introduced multiple effective methods to this approach such as
mechanical stripping, epitaxial growth, chemical stripping [42] and hot
solvent. Zhang et al. [43] reported a novel pyridine–thermal strategy
for successive exfoliation and reduction of graphite oxide with the use
of pyridine as the intercalating agent and dispersant, and the obtained
graphene exhibits a good performance in capacitive deionization.
The graphene lamellar structure of GO is approximately 1–30 μm
thick and possesses a collection of oxygen-rich functional groups (car-
boxyl and hydroxyl) on its edges and planes [44]. The presence of
oxygen-containing functional groups makes the structure of GO very
complex and also imparts many valuable properties. For example, GO
can be stably dispersed in water without dispersants and stabilizers,
which can be very convenient for subsequent processing [45]. Oxygen-
containing functional groups are prone to chemical reactions, which
can be used to make various chemical modifications on the surface of
GO [46].
The GO preparation method was conceived 150 years ago. Brodie
obtained graphite oxide through repeatedly treating graphite with ni-
tric acid and potassium chlorate. Staudenmaier then developed this
oxidation method with concentrated sulphuric acid, nitric acid and
potassium chlorate. Subsequently, Hummers improved it with con-
centrated sulphuric acid, sodium nitrate and potassium permanganate.
Hummers' method became the most widely used procedure because it is
N. Song et al.
safe and time efficient. After the oxidation reaction, brown oxidation
graphite can be obtained from graphite powder, and then GO is ex-
tracted by ultrasonic or high shear intense agitation stripping.
Presently, many researchers [47–49] have adapted this method to
procure different sized lamellar structures by adjusting the amount of
oxidant and oxidation time. In recent years, the ionic liquid auxiliary
electrolytic stripping method [50], potassium ferrate [51], sealed oxi-
dation [52] and other new methods are also emerging, thus ensuring
that the safety, promptness and environmental protection of GO oxi-
dation can be vastly improved.
3.2. Preparation of GBSM
Due to the repulsive effect of the large π-bond orbital electron
clouds in graphene, single-graphene is not permeable to water mole-
cules or gas molecules [53]. This means that graphene desalting
membrane preparation method can be divided into two types. In the
first process, the preparation of single-layer nano-porous graphene
(porous graphene membrane, PGM) uses nanopores to achieve desali-
nation. In the second, the assembly of graphene layer by layer (layered
GO membrane, LGOM), using a two dimensional nano-channel between
adjacent GO layers achieves desalination. Both can control the se-
paration performance of the graphene separation membrane by mod-
ification of the size of nanopores or the interlayer spacing of GO.
3.2.1. Preparation of porous graphene film
In 2008, Liu et al. [54] from Columbia University produced GO with
nanopores using high-temperature atmospheric oxygen. They en-
capsulated graphene (prepared by mechanical stripping) into a mullite
tube with a gas inlet and outlet, then placed the tube into a tubular
furnace at a certain temperature while passing over it a gaseous mixture
of oxygen and argon. Following that process, nanopores can be pre-
pared by controlling the flow rates of Ar and O2 gas (1.1 and 0.86 L/
min, respectively), oxygen partial pressure (350 Torr) and reaction time
(usually 2 h). This laid the foundation for the preparation of porous
graphene. In the same year, Fischbein et al. [55] found that focused
electron beam irradiation could be used to make nanopores. In a
transmission electron microscope (TEM), graphene was bombarded
with a focused electron beam, then stable nanopores could be prepared
in a few seconds. Pore size could be controlled from 0.2 nm to tens of
nanometres. Fig. 5 shows TEM images of a suspended graphene sheet.
The structure of the pores prepared by this method does not change
with time and the presence of pores does not distort the graphene
structure. Additionally, the graphene nanosheets do not fold, wrinkle,
curl or deform in the focal plane during the etching process [54].
However, since the preparation of the nanopores is required in the
TEM, the size of the prepared porous graphene is small, making it
Fig. 5. TEM images of a suspended graphene flat: c) High-definition image of the nanopore. d) Image of multiple nanopores [55].
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Desalination 437 (2018) 59–72
difficult to carry out large-scale preparation. Bell et al. [56] used a
gallium ion or helium ion beam to bombard graphene, which could
make holes approximately 20 nm in diameter. Russo and Golovchenko
et al. [57] used argon ions to bombard graphene, preparing porous
graphene with nanopores with a diameter range of 0.15–1.35 nm.
In addition, there are hydrogen (oxygen) plasma etching methods
[58–60], ozone/ultraviolet light irradiation oxidation [61–63], and
gold catalytic oxidation [64]. R. Yang et al. [58] used a hydrogen
(oxygen) plasma etching method to etch graphene. In this method, the
carbon atoms in graphene were hydrogenated by hydrogen plasma,
thereby generating CH4 and then it was spilled out to form nanopores.
We can control the hole size (up to several hundred nanometres) and
the shape of the hole by controlling the etching parameters (such as
plasma density, temperature, time). This simple, clean and controllable
method is expected to achieve a large-scale yield of GO. Similarly, Zhao
et al. [65] prepared a graphene nano-foam with a pore-layered struc-
ture by hydrothermal self-assembled of GO nanoparticle-induced
etching process with local positioning. Fig. 6 is a SEM and STEM image
of graphene nanomesh assembled foam (N-GMF). This new GMF is rich
in transport channels and available graphene edges, which provide
suitable application materials for future high performance functional
devices.
3.2.2. Preparation of GO separation membrane
At present, there are various methods to prepare GO separation
membranes such as filtration, coating, evaporation, layer by layer self-
assembly and electric field induced assembly. The filtration method
consists of dispersing GO on the porous membrane (usually ultra-
filtration membrane or microfiltration membrane) as the substrate,
under pressure [66] or in a vacuum [67,68], then filtering, drying [66]
and other post-processing to obtain the membrane with the porous
support layer. Han et al. [69] prepared the MWNT-intercalated gra-
phene nanofiltration membrane (G-CNTm). The dispersion of rGO (re-
duced grained graphene) and CNT was filtered within a vacuum in a
polyvinylidene fluoride (PVDF) UF membrane (effective 100 mm dia-
meter), resulting in the G-CNTm. The method can be used to prepare
the GO film whose thickness is from several nanometres to several
microns. But the interface between adjacent layers is weak, thus leading
to poor stability.
The coating methods include cloth-coating, spin-coating, spray-
coating, with the spin-coating method being the most commonly used.
Self-assembled GO nanosheets are in high demand. A new type of
composite NF membrane was prepared by coating the thin layer of
ethanol gel (GC) on poly (acrylonitrile) (PAN) ultrafiltration membrane
[70]. First, a certain amount of GC (0.6 to 1.8 wt%) was dissolved in
deionized water to prepare a casting solution. The casting solution,
filtrated by a G3 sand filter, was then daubed on a surface-dried PAN UF
N. Song et al.
Fig. 6. SEM and STEM image of N-GMF [65].
membrane with a glass rod. This method is currently more prevalent
and generally uncomplicated.
The GO film prepared by the evaporation method is generally car-
ried out at the gas-liquid interface, and the greater the thickness, the
easier it is to obtain a membrane with a large transverse size. Yang et al.
[71,72] prepared GO in a larger concentration (~2 mg/mL) solution, by
evaporating it to remove the solvent, then obtained the self-assembled
GO film on the surface. By controlling the evaporation temperature and
time, it is possible to effectively control the thickness of GO.
GOs rich in carboxyl, hydroxyl and epoxy groups use layer by layer
(LBL) self-assembly. In one case, self-assembly is used between the
negatively charged characteristics of carboxyl and positively charged
organic matter; while in another scenario, the appropriate reactive
functional groups were selected for chemical cross-linking self-as-
sembly, utilizing the reactivity of these oxygen-containing functional
groups. Rich carboxyl groups on the surface of GO will negatively
charge those dispersed in the water. Therefore, it can be directed to
move in the electric field, which provides feasibility for the self-as-
sembled film. Zhao et al. [73] fabricated GO-based ultrathin hybrid
membrane via LBL self-assembly. After a section of layering and cross-
Fig. 7. Schematic of the reaction mechanism in multilayer membrane by LbL self-assembly [73].
65
Desalination 437 (2018) 59–72
linking, the basement membrane is compounded with multiple layers of
gelatin (GE) and GO. Fig. 7 is schematic of the reaction mechanism in
multilayer membrane by LBL self-assembly.
4. Application
Due to its superior performance, membrane separation technology
is now receiving attention globally. In the light of energy tension, re-
sources shortages, the deterioration of the ecological environment,
membrane processes have been considered as a vital new technology in
the 21st century within the field of industry and technology.
Subsequently, the prospect of GBSM has become a central issue. As the
application of GBSM technology is still emerging, much work has been
done to improve this technology. In the past decade, GBSM technology
has developed extensively and has been used internationally for sea-
water desalination, preparation of pure and ultrapure water, medicine,
biology, environmental protection and many other fields. This pro-
mising technology with significant economic, social and environmental
benefits will continue to have a substantial impact worldwide. At pre-
sent, the practical driving force of graphene-based membranes can be
N. Song et al. Desalination 437 (2018) 59–72

categorised into pressure, concentration difference and electricity.

4.1. Pressure-driven membrane process

The pressure-driven membrane process refers to the process of se-

parating the permeate from the retentate, with pressure as the driving
force. The separation membrane is a pressure-driven membrane [74].
There are several types of pressure-driven membranes, including NF,
UF, MF and RO. According to a global market report, RO is the most
widely used membrane, accounting for approximately 45%. NF and UF
combined equate to 20% and MF accounted for 30%. A graphene-based
membrane allows for adequate desalination mainly due to its two-di-
mensional nanochannel between adjacent GO layers and adjustable
nanoporous surface. Subsequently, it is very common to use graphene-
based membranes as pressure-driven membranes. Fig. 9. Water permeability scales roughly linearly with the area of hydroxylated or hy-
Molecular dynamics simulation (MDS) is an effective method within drogenated pores [75].
nanotechnology research and it has been instigating a great deal of
interest. In the same way, simulation calculations have proven that
purification assessed the potential of rGOs. The relationship between
graphene-based materials have many advantages concerning mem-
rGO synthesis parameters and defect size can be used to control the size
brane separation techniques. Cohen-Tanugi et al. [75] demonstrated
of nanopores in rGO. The results show that the rGO film prepared under
that monolayer nanoporous graphene (NPG) membranes can success-
appropriate conditions can enhance effective separation and the level of
fully remove salts from water. MDS was used to predict that single-layer
water flux.
NPG membranes could enhance water delivery capacity to 66 L/
Reverse osmosis was first invented by Reid in the United States in
(cm2·day·MPa). In contrast, the capacity of water delivery using the
1953, and then improved jointly by Loeb and Sourirajan in 1960. That
typical reverse osmosis membrane was approximately 0.01–0.05 L/
same year, the world's first asymmetric acetate fibre semipermeable
(cm2·day·MPa). The rapid flow rate of water was attributed to the
membrane with high desalination rate and high permeability was
atomic thickness of the graphene film. Fig. 8 is a conceptual illustration
formed. The spacing between the GO nanolamellars can become a water
of nanoporous graphene rejecting NaCl and Fig. 9 illustrates computed
channel that allows water molecules to pass quickly, thereby increasing
water permeability for nanoporous graphene functionalized with hy-
the water flux. As opposed to using a pure graphene membrane, it is
drogen and hydroxyl groups for various pore sizes. Water permeability
common to mix graphene with a common membrane material as a
scales are arranged in a generally linear array within the area of hy-
functional material, expanding the water channel by increasing the
droxylated or hydrogenated pores. Cohen-Tanugi et al. used monolayer
graphene content, thereby intensifying the water flux. Yin et al. [79]
graphene as a reference to explore the possibility of multilayer NPG as a
doped GO nanosheets into thin film nanocomposite (TFN) RO mem-
desalinated RO membrane using molecular dynamics simulations [76].
brane by in situ interfacial polymerization. As a result, the GO na-
A multilayer NPG film with the equivalent thickness of the polyamide
nosheet revealed good dispersibility and the membrane structure was
film (~200 nm), consists of about 200 graphene layers. The 200-layer
improved. When the GO concentration in the membrane increased from
NPG film has a permeability of about 2 L/(m2·h·bar), which is the same
0 to 0.015 wt%, the permeate flux increased from 39.0 ± 1.6 to
as that of a typical polyamide film. In addition, Konatham et al. [77]
59.4 ± 0.4 L/m2·h at 300 psi. NaCl and Na2SO4 rejection slightly de-
studied the transport of water and ions in the pores of the graphene
creased from 95.7 ± 0.6% to 93.8 ± 0.6% and 98.1 ± 0.4% to
sheet using molecular dynamics simulations. The simulation results
97.3 ± 0.3%, respectively. Fig. 10 is permeate flux and salt rejection of
show that the use of hydroxylated narrowly graphene pores can effec-
GO TFN membranes. Although many researchers have prepared two
tively retain Cl− even under medium ionic strength, which means the
kinds of particles doped desalination films, these membranes often have
model can be used for desalination. Lin et al. [78] used molecular dy-
dual characteristics. Safarpour et al. [80] prepared a thin film nano-
namics techniques to understand the formation of defects in rGO and its
composite reverse osmosis (TFN-RO) film embedded in the polyamide
separation performance in desalination. In addition, natural gas

Fig. 10. Permeate flux and salt rejection of GO TFN membranes. The concentration of salt
Fig. 8. Conceptual illustration of nanoporous graphene rejecting NaCl [75]. solution is 2000 mg/L and the TMP is 300 psi [79].

66
N. Song et al. Desalination 437 (2018) 59–72

its composites were applied to the RO membrane, giving us an under-

standing of the structure, properties and potential research applications
of graphene. Graphene is highly valuable in the RO membrane.
Nanofiltration is a molecular separation technique that occurs be-
tween ultrafiltration and reverse osmosis. It has a certain retention rate
for inorganic salts because its surface separation layer is composed of
polyelectrolytes. It has different rejection rates for different valence
particles. Graphene-based membranes can also be fabricated to be used
for nanofiltration. For example, Wang et al. [81] used graphene on
polyacrylonitrile nanofiber mats to create a novel GO nanofiltration
membrane (GO@PAN). It was found that with the increase of the GO
thickness, the water flux decreased sharply, the cause of which can be
simply explained as an increase of mass transfer resistance (as shown in
Fig. 12). However, when the thickness of GO reached 34 nm, the
maximum water flux (8.2 L·m−2·h−1·bar−1) of the film was 1.6 times
[82] higher than the previous 33 nm GO film (water flux
5.0 L·m−2·h−1·bar−1). Such a high-water flux can be explained by the
Hagen−Poiseuille theory. In this case, the GO sheet can be seen as a
carbon wall, and the gap between the GO sheets can be seen as a 2D
channel. [83–85]. Based on the hydrophobicity of the carbon wall in
the GO and the slip flow theory, the reason why the water flux becomes
larger can be explained more appropriately. Water enters the edge or
the defects of the GO nanosheets (hydrophilic “gate”), and then slip into
the 2D nanometre channel due to the hydrophobicity of the carbon
wall. Fig. 13 shows the diagram of the hydrophilic “gate” and hydro-
phobic nanochannels. Zinadini et al. [86] prepared a novel poly-
ethersulfone (PES) doped with GO nanosheets via the phase inversion
method. The water flux from the nanocomposite membranes improved
significantly after addition of GO to the casting solution, due to the
higher hydrophilicity of the prepared membranes. They found that the
GO membranes have higher dye removal capacity than the unfilled PES
Fig. 11. (a) Water flux and (b) salt rejection of thin film nanocomposite reverse osmosis
and showed noteworthy reusability during filtration.
membrane modified by reduced graphene oxide/TiO2 [80]. Ultrafiltration is widely used in the concentration, separation and
purification of certain solutions with low molecular weight soluble
solutes and high molecular substances. With the continual improve-
layer with rGO/TiO2 nanocomposites through interfacial polymeriza-
ment of membrane materials and process technology, ultrafiltration in
tion. The aim was to improve the film's antifouling performance and
the field of water treatment technology has been widely used.
chlorine resistance. The experimental results showed that the RO
Incorporating graphene-based materials into the ultrafiltration mem-
membrane flux was 51.3 L/m2·h and salt rejection was 99.45% when
brane is an area of great interest to many researchers. For example,
the 0.02 wt% rGO/TiO2 nanocomposites are doped. Therefore, the
Vatanpour et al. [87] chose two nanoparticles namely, rGO and Ag.
performance of rGO/TiO2/RO film is excellent. After chlorination tests,
First, the rGO/Ag nanocomposites were added at all concentrations as
the salt rejection of bare RO membrane was reduced by 30%, while for
opposed to only the solitary PES, and the static contact angle clearly
0.02 wt% rGO/TiO2/RO membrane, the salt rejection decreased by only
decreased. The reduction in contact angle statistics shows an increase in
3%, indicating that after doping rGO/TiO2 nanocomposite, the chlorine
hydrophilicity, which means that the water flux has been influenced.
resistance is improved. Fig. 11 is the water flux and salt rejection of the
The results also showed that 0.2 wt% of rGO/Ag nanosheets' water flux
TFN-RO membranes. We reviewed many cases in which graphene and
increased from 220 to 429.8 kg/m2·h, as compared to that of the

Fig. 12. (a) Relationship between pure water flux and GO layer thickness (operated under 1.0 bar); (b) water flux relative to pressure applied on the GO@PAN membrane with a GO
thickness of 160 nm [80].

67
N. Song et al.
Fig. 13. Schematic of hydrophilic “gate” and hydrophobic nanochannels [81].
Fig. 14. Pure water flux of rGO/Ag embedded PES membranes [87].
isolated PES (as shown in Fig. 14). Secondly, rGO/Ag also displays an
efficient antifouling performance. The pure PES film is the most prone
to irreversible fouling with an irreversible fouling ratio of 51.7%, ac-
counting for about 88% of the total fouling. The addition of a small
number of rGO/Ag nanocomposites can effectively reduce the irrever-
sible fouling ratio. Graphene-based UF membranes can also be fabri-
cated under mild conditions by immersion precipitation and solvent
evaporation. Fryczkowska et al. [88] suggested that the addition of GO
nanomaterials to the polymer film matrix would affect the pore for-
mation process and that the addition of GO would also reduce the static
contact angle of the membrane, thereby improving the hydrophilicity.
The film formed by coagulation in distilled water has a higher porosity,
better hydrophilicity and permeability than the film obtained by sol-
vent evaporation. Table 2 shows the performances comparison of dif-
ferent pressure-driven membranes. Table 3 displays the synthesis
methods of several kinds of pressure-driven graphene composite
membranes and their performances.
68
Desalination 437 (2018) 59–72
4.2. Concentration-driven membrane process
Forward osmosis is a concentration-driven membrane process in
which water flows from the diluted feed solution to the concentrate
through a semipermeable membrane. Forward osmosis membranes,
which do not need to apply pressure as a driving force, have become a
focal point of conservational separation technology. At present, forward
osmosis membrane technology is often used for desalination pre-treat-
ment. Gai et al. [107] used monolayer porous graphene as a FO
membrane and studied the properties of the membrane using molecular
dynamics simulation. The results showed that the water flux of the
membrane is 28.1 L/cm2·h, which is about 1.8 × 104 times higher than
that of the cellulose triacetate membrane. This may be a potential op-
portunity for FO desalination, power generation and other procedures.
However, the above researchers did not consider whether the graphene
perforation was uniform and whether the mechanical strength of the
perforated graphene sheet was still adequate. Consequently, there is a
long way to go to achieve pure graphene FO membranes. In addition,
researchers recently used porous graphene composites as modifiers for
the preparation of TFC polyamide FO membranes [108]. The permeate
flux of the TFC membrane doped with 0.5 wt% of the reduced graphene
oxide modified graphite carbonitride (CN/rGO) was 41.4 L/m2·h (2 M
NaCl as draw solution, deionized water as feed) which was about 20%
higher than that of the bare TFC membrane (as shown in Fig. 15). This
study shows that CN/rGO can be used as an additive for porous sub-
strates, and can prepare a superior quality FO membrane. Table 4 shows
several concentration-driven graphene composite membranes and their
permeation performance.
4.3. Electric-driven membrane process
Electrically-driven membrane processes, especially electrodialysis,
are important operations within the field of desalination [110]. GO has
recently been used in fuel cells as an effective electro-catalyst for
oxygen reduction reactions [111]. This indicates that the hydrogen
N. Song et al. Desalination 437 (2018) 59–72

Table 2 reorganization in an electric field is also involved in the oxygen re-

Performances comparison of different pressure-driven membranes. duction reaction (ORR)), it can be speculated that GO may also be a
water dissociation catalyst. The insertion of GO in BPM IL provides a
NO. Materials Process Water flux Salt rejection (%) Ref.
(L/m2·h·bar) unique way to evaluate the catalyst for this reaction [114]. In addition,
NaCl Na2SO4 the graft modification of the GO surface can be carried out by hydroxyl,
epoxy, ketone and carboxylic acid groups. GO provides proton con-
1 PSf NF 4.83 30.44 86.43 [89]
duction through the Grotthuss mechanism and indicates that the water-
2 PEI–copper(II) NF 2.32 43.5 68.3 [90]
complex retention properties of composite PEM (polymer electrolyte membrane)
3 IPC/ICIC RO 2.63 95.8 – [91] were enhanced [115]. Pandey et al. [116] prepared PEMs by using
(2.0 wt%) different wt% SIGO (Sulphonated imidized graphene oxide) and sul-
4 TMC/MPD RO 1.13 98.0 ± 0.3 – [92] phonated poly(imide) (SPI). The results showed that SPI/SIGO com-
5 CFIC/MPD RO 1.33 96.8 ± 0.3 – [92]
posite PEMs improved thermal stability, mechanical strength, oxidation
6 NOCC/PS NF 3.00 42.7 – [93]
(1.0 wt%) resistance and good water retention. Table 5 shows several electric-
7 GC/PAN NF 1.06 – 87.4 [70] driven graphene synthesis methods of composite membrane and para-
(0.6 wt%) meters.
8 Zeolite RO 1.37 93.9 ± 0.3 – [94]
9 Silica RO 0.87 95.1 – [95]
10 MCM-41 RO 2.25 97.9 ± 0.3 – [96] 5. Conclusions and outlook
11 MWNTs RO 1.75 90 ± 0.3 – [97]
Graphene is a novel material with many essential properties that
Abbreviations: PSf: polysulfone; PEI: polyethyleneimine; IPC: isophthaloyl chloride; ICIC: enable an effectual performance within the context of desalination. Its
5‑isocyanate-isophthaloyl chloride; CFIC: 5‑chloroformloxy-isophthaloyl chloride; MPD:
excellent mechanical characteristics, single atomic layer structure, large
m‑phenylenediamine; NOCC: N,O‑carboxymethyl chitosan; PS: polysulfone.
specific surface area and rich modification approaches are irreplaceable
advantages in the field of desalination. In this article, we provide a
bonds of the bulk water in contact with the surface of the oxide material
comprehensive review of the recent advances of the applications of
lead to proton transfers [112], resulting in a decrease in the activation
GBSMs. The fabrication of all kinds of GBSMs, including porous gra-
barrier in the dissociation of water molecules [113]. Due to this general
phene films and GO separation membranes, are discussed and the re-
water dissociation (WD) mechanism with oxides (and as OeH bond
lated synthetic methods are summarised. The application of the GBSMs

Table 3
The synthesis methods of several kinds of pressure-driven graphene composite membrane and their performances.

NO. Materials Process Methods Water flux Salt rejection (%) Ref.
(L/m2·h·bar)
NaCl Na2SO4

1 GO-TFN RO Coating method 2.871 93.8 ± 0.6 97.3 ± 0.3 [79]

(0.015 wt%)
2 GO-PSBMA/PES NF Interfacial polymerization 11.98 4.3 ± 0.3 9.0 ± 0.3 [31]
(22.0 wt%)
3 GO@PAN NF Filter method 8.20 9.8 56.7 [81]
4 G-PANCMI UF Blending method 978 ± 27 – – [32]
5 PSf-GO NF Coating method 2.45 59.5 95.2 [41]
(0.30 wt%)
6 rGO–CNT-AAO NF Vacuum-assisted filter 31.5 42 ± 0.6 84 [98]
7 (GE/GO)/H-PAN NF Layer by layer self-assembly 2.275 – – [73]
(87.8 wt%)
8 GO−OCMC/PSf NF Layer by layer self-assembly 1.78 ± 0.02 62 92.9 [99]
9 rGO/Ag-PES UF Phase Inversion method 107.45 – – [87]
(0.2 wt%)
10 GO-PSf NF Coating method 5.47 33.01 89.79 [89]
11 rGO/TiO2-PSf NF Coating method 6.14 36.61 93.57 [89]
(0.01 wt%)
12 rGO/TiO2 RO Interfacial polymerization 3.42 99.45 – [80]
(0.02 wt%)
13 Co3O4-GO-PES UF Blending method 347.9 – – [100]
(1.5 wt%)
14 GOAg-PAA UF Layer by layer self-assembly 396.1 ± 58.4 – – [101]
15 GOTI-PAA UF Layer by layer self-assembly 453.5 ± 30.8 – – [101]
16 GO-Ly/PSF UF Blending method 318.0 – – [102]
17 CRGO-Ly/PSF UF Blending method 372.3 – – [102]
18 GO-TFC RO Interfacial polymerization 1.07 99.5 ± 0.3 – [103]
19 PVDF/GO UF Immersion precipitation 157.48 – – [88]
(0.5 wt%)
20 PES/GO NF Blending method 8.87 – – [86]
(0.5 wt%)
21 PEI-GO/BPPO UF Blending method 532.5 – – [104]
(0.60 wt%)
22 PVDF/GO/PVP UF Blending method 90.0 – – [105]
(0.5 wt%)
23 PVDF/GO UF Blending method 94.0 – – [106]
(0.1 wt%)

Abbreviations: TFC: thin film composite; AAO: anodic aluminum oxide; OCMC: O‑(Carboxymethyl)‑Chitosan; PAA: polyallylamine; PEI: polyethyleneimine; BPPO: brominated poly
(2,6‑dimethyl‑1,4‑phenylene oxide); PVP: polyvinylpyrrodione.

69
N. Song et al. Desalination 437 (2018) 59–72

Fig. 15. (a) Water flux and (b) reverse salt flux of TFC membranes in FO mode with varying draw solution concentration [108].

Table 4 of the GO sheet surface are narrowed during the compaction process,
Several concentration-driven graphene composite membrane synthesis and their per- resulting in a change in the structure of the support film and the GO
meation performance.
sheet. This indicates that a portion of the water channels in the wrinkles
No. Materials Methods Water permeability Ref. have a smaller cross-sectional area and a higher permeation resistance
(L/m2·h) [121]. In addition, the following difficulties need to be solved: drilling
on graphene film is a difficult procedure because it is an expensive and
1 PES–CN/rGO Coating method 41.4 [108]
complex process. It can also produce uneven holes unforeseen variables.
(0.5 wt%)
2 GO/Ag-TFC Layer by layer self- 5.25 [109]
GO can also be difficult to integrate with polymers. Subsequently, the
assembly direct preparation of a GO layer on a highly porous nanofibrous mat is
3 Porous Layer by layer self- 2810 (molecular dynamics [107] still a challenge. In most solvents, GO is easy to aggregate and difficult
graphene assembly simulation) to obtain effective dispersion. Researchers are trying to overcome these
difficulties. Notwithstanding, the impact of graphene-based membranes
will remain at the forefront of research as it has the potential to develop
is introduced and their performances are listed and compared. When
further and gain widespread recognition. It is clear that graphene and
GBSMs are used as pressure-driven membranes, they frequently have a
its derivatives will continue to have a significant role within the context
high water flux, good antibacterial and anti-pollution performance.
of desalination technology.
Although there are a few cases of GBSMs which are used as electric-
driven membranes, they are very promising because their stability and
efficient water-retention. However, it would appear that graphene
Acknowledgements
contributes very little within the realm of forward osmosis and the
amount of research concerning this collaboration reflects this. This may
We gratefully acknowledge financial support from the National Key
be because it fails to perform as well as it does in reverse osmosis.
Research and Development Projects (No. 2017YFC0403901), the
It is said that anything can be a double-edged sword. Graphene has
National NSF of China (No. 21576250) and the Public Science and
numerous shortcomings in membrane separation technology. For ex-
Technology Research Funds Projects of Ocean (No. 201505021). We
ample, the mechanical strength of single layer graphene is very weak.
also acknowledge the financial support of the Taishan Scholar Program
Our lab found that the compacted GO membrane flux attenuation was
of Shandong Province.
faster than conventional NF or RO membranes. After a number of ex-
periments and characterizations, we have confirmed that the wrinkles

Table 5
Several electric-driven graphene synthesis methods of composite membrane and parameters.

No. Materials Methods Water uptake Ion-exchange capacity (IEC) Swelling ratio Proton conductivity km × 10−2 Ref.
(%) (meq/g) (%) (S·cm−1)

1 GO−BPMs Spin-coated – – – – [114]

(bipolar membranes)
2 SPI/SIGO Blending method 95.61 2.24 12.37 11.38 [116]
(15.0 wt%)
3 SPI/FGO Blending method 47.2 – – 7.72 [117]
(0.05 wt%)
4 PBI/ZC-GO Coating method 35.2 1.12 5.23 1.95 [118]
(25.0 wt%)
5 NSBC/NMPSGO Blending method 69.98 2.09 19.15 8.87 [119]
(39.0 wt%)
6 NSBC/GO-8 – 32.76 1.23 15.18 5.28 [119]
7 CS/S4GO Blending method 54.7 – 25.9 2.67 [120]]
(2.0 wt%)

Abbreviations: BPMs: Bipolar membranes; FGO: functionalized graphene oxide; PBI: polybenzimidazole; ZC-GO: zwitterion-coated graphene oxide; NSBC: N‑o‑sulphonic acid benzyl
chitosan; NMPSGO: N,N‑dimethylene phosphonic acid propylsilane graphene oxide; CS: chitosan; SGO: sulfonated graphene oxide.

70
N. Song et al.
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