Chemical Engineering Journal 422 (2021) 130082

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Chemical Engineering Journal

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

Review

MoS2-based membranes in water treatment and purification

Yang Liu a, c, Yingcan Zhao b, d, *, Xinbo Zhang a, c, Xuanlin Huang a, c, Wenchao Liao e, f,
Yintong Zhao a, c
a
Joint Research Centre for Protective Infrastructure Technology and Environmental Green Bioprocess, School of Environmental and Municipal Engineering, Tianjin
Chengjian University, NO.26, Jinjing Rd, Xiqing District, Tianjin 300384, PR China
b
Department of Biomedical Engineering, Southern University of Science and Technology, No. 1088 Xueyuan Rd, Nanshan District, Shenzhen, Guangdong 518055, PR
China
c
Tianjin Key Laboratory of Aquatic Science and Technology, School of Environmental and Municipal Engineering, Tianjin Chengjian University, NO.26, Jinjing Rd,
Xiqing District, Tianjin 300384, PR China
d
Graduate School at Shenzhen, Tsinghua University, Shenzhen, Guangdong 518055, PR China
e
College of Health and Environmental Engineering, Shenzhen Technology University, No.3002 Lantian Rd, Pingshan District, Shenzhen, Guangdong 518118, PR China
f
School of Environmental Science and Engineering, Xiamen University of Technology, Xiamen, Fujian 361024, PR China

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

Keywords: Membrane separation technologies have proven viable in tackling the issues of water pollution and shortage of
Water treatment freshwater resources with practical applications. Two-dimensional (2D) materials with thickness of one to a few
Membrane separation atoms stand out as desirable building blocks to design and fabricate membranes with outstanding performances.
MoS2-based membrane
Molybdenum disulfide (MoS2), as a promising alternative 2D material, has been currently one of the most
MoS2 nanosheets
intriguing 2D materials beyond graphene due to many excellent physicochemical, mechanical and biological
properties, which are not available in graphene-based nanomaterials. However, to the best of our knowledge,
there has been few reviews of MoS2-based membranes studies. It is thus urgently needed to summarize key
findings of MoS2-based membranes and assess the current research studies in this area. This paper attempts to
critically review the present state-of-the-art of MoS2-based membranes in water treatment and purification.
Firstly, we briefly introduce the main preparation methods of MoS2 nanosheets, which are often applied in
fabricating membranes. Next, the design and fabrication of MoS2-based membranes are systematically summa­
rized in terms of nanoporous membranes, layer-stacked membranes, MoS2 composite membranes including
MoS2-incorporated membranes, and membranes surface modification with MoS2. Then, we critically review the
recent advancement about applications of MoS2-based membranes for water treatment and purification, focusing
on desalination, industrial wastewater treatment, and antifouling properties. Finally, we discuss the existing
challenges, future research efforts and opportunities of MoS2-based membranes. This work will be very valuable
to understand the current state-of-the-art of MoS2-based membranes and will be helpful for developing other 2D-
based membranes for efficient and low-energy-consumption in water treatment and purification.

1. Introduction maintenance can be achieved, while pollutants could be removed

Increasing water pollution and shortage of freshwater resources due
to urbanization, population growth, misuse, agricultural and industrial
activities and climate change have become global environmental issues
[1]. Over the past several decades, membrane separation technologies
have proven viable in tackling these issues with practical applications
[2,3], such as drinking water purification, municipal and industrial
wastewater treatment and reuse, desalination and water-related appli­
cations. With membrane technologies, high water quality with easy
without addition of chemicals or generation of toxic byproducts, sta­
tionary parts with compact modular construction and so forth [2-5].
However, as well-known, membranes suffer a ubiquitous trade-off be­
tween permeability and selectivity, i.e. highly permeable membranes
sacrifice selectivity and vice versa, as well as the inevitable membrane
fouling during the operation of membrane units. The conventional
membrane materials (often used for making porous and/or dense
membranes) and empirical fabrication methods of membranes are
difficult to bring huge revolutionary changes to the significant

* Corresponding author.
E-mail address: zhaoyc@sustech.edu.cn (Y. Zhao).

https://doi.org/10.1016/j.cej.2021.130082
Received 10 January 2021; Received in revised form 24 March 2021; Accepted 24 April 2021
Available online 3 May 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
Y. Liu et al.
improvement of membrane performance.
In recent years, the nanomaterials with unique properties have been
used to develop novel technologies of water treatment and purification
or improve the efficiency of existing water treatment processes [1].
Among them, two-dimensional (2D) materials with thickness of one to a
few atoms stand out as desirable building blocks to design high-
performing membranes. The 2D nanomaterials open up a new way for
rapid development of membranes that are impossible with conventional
membranes materials. The 2D material-based membranes made from
atomic thickness are easier to control the surface properties and internal
structure of membranes such as thickness, morphology, hydrophobicity,
water transfer channel, chargeability, charge density and so forth [6-
14]. Moreover, the multifunctional membranes could be fabricated by
utilizing the advantages of nanomaterials, which are naturally func­
tional and easy to modify on the surface, to achieve the goal of more
than membrane separation. Therefore, extensive studies have demon­
strated that 2D material-based membranes exhibit high permeability,
good selectivity, and antifouling ability [1,7,15-17].
Currently, graphene and its derivatives such as graphene oxide (GO)
and reduced graphene oxide (rGO)) are the most widely studied class of
2D materials for fabricating 2D-based membranes with high perfor­
mance. In the past few years, other types of 2D materials such as mo­
lybdenum disulfide (MoS2) [18], MXene [19], boron nitride [20],
metal–organic frameworks (MOF) [21], and covalent organic frame­
work (COF) [22] are rapidly emerging while developing membranes
materials. Among them, MoS2 nanosheets have been widely involved in
membrane design and applications for the water-related treatment. Both
MoS2 nanosheets and MoS2-based membranes have many advantages.
MoS2 had relatively higher elastic modulus (200–300 GPa [18])
compared with other nanomaterials (GO: 207.6 ± 23.4 GPa [23], MOF:
3–7 GPa [24]), which facilitate to prepare the water treat membranes.
Similar to graphene which made from graphite, MoS2 could be obtained
from natural molybdenite mineral [25], while MOF/COF must be
chemically synthesized. Moreover, current studies have shown that
MoS2 performs better than graphene in many aspects such as catalysis,
electrochemical properties and etc [18,26,27]. The excellent physi­
ochemical properties of MoS2 endow the fabrication of multi-functional
MoS2 membranes. On the other hand, it revealed that MoS2 membranes
were more stable than GO membranes in aqueous solution [15]. Besides,
one study showed monolayered MoS2 performed 27% better than gra­
phene, 38% than phosphorene, 35% than boron nitride, and 20% than
MoSe2 in aspect of water permeability while keeping ion rejection rate
of >99% (Fig. 1) [28]. Sun et al., [29] reported the MoS2 membrane
possessed a water flux of 245 LMH/bar and evans blue rejection of 89%.
The water flux was 3–5 time higher than that of GO membranes. Overall,
MoS2-based membranes have been proved to possess excellent mem­
brane performance with enhanced simultaneous permeability and
selectivity [15,30-34], enable multifunctional properties [35-38] and
Fig. 1. (a) ion rejection and water permeability of five different 2D-based membranes. (b) The drilled nanopores (~50 Å2) in different 2D-based membranes [28].
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Chemical Engineering Journal 422 (2021) 130082
antifouling ability [8,15,39,40], and so forth.
Until now, there are many review articles in summarizing graphene-
based membranes in classification of membranes, membranes fabrica­
tion and characterization, separation mechanism and the improvement
of membrane performance [1,3,11,12,41-44]. Undoubtedly, there exists
significant discrepancy between graphene-based membranes and other
types of 2D-based membranes considering their laminated structure,
physicochemical and mechanical properties such as elemental compo­
sition, hydrophilicity, surface properties, interlayer spacing, the inter­
layer force and so forth. A few reviews on the design and preparation of
membranes by other 2D-based membranes (e.g. MXene, MOF and COF
based membranes) for water treatment and purification have been
released [9,19,24,45]. Extensive studies on MoS2-based membranes
have been conducted for the past few years. MoS2-based membranes are
being involved in various separation processes such as nanofiltration
(NF) [13] , reverse osmosis (RO) [46] and forward osmosis (FO) [47].
However, to our best knowledge, there has been few reviews of MoS2-
based membranes studies. Which types of the MoS2-based membranes
commonly include in water treatment and purification? And what is
difference and similarity as compared to GO-based membranes? How
will the defects on the planar of MoS2 nanosheets affect the membrane
permeability and selectivity, whether the defects will favor to the
development of multifunctional (e.g. adsorptive and catalytic) mem­
branes, and what will be removal mechanisms for various contaminants
in aqueous solution. Additionally, it seems that there may exist some
controversial research results including theoretical prediction and
experimental studies, as well as the differences in experimental results
from various studies. For example, the fully hydrated MoS2 membranes
with a 1.2 nm interlayer spacing had moderate-to-high water perme­
ability and ionic rejection [15], while another study reported the sep­
aration layer of MoS2 nanosheet frameworks without tunability did not
possess water-salt selectivity [8]. It is thus urgently needed to summa­
rize key findings of MoS2-based membranes and assess the current
research status for understanding separation mechanism and improving
membrane performance in water treatment and purification.
In this review, we first discuss the main preparation methods of MoS2
nanosheets relevant to membrane fabrication. Next, the fabrication and
design of MoS2-based membranes are systematically summarized in
terms of nanoporous membranes, layer-stacked membranes, MoS2
composite membranes including MoS2-incorporated membranes, and
membranes surface modification with MoS2. The summary is mainly
based on the comprehensive consideration of the current development
of 2D-based membranes and the classification of traditional membrane
technologies. Then, we critically review the recent advancement about
applications of MoS2-based membranes for water treatment and purifi­
cation, focusing on desalination, industrial wastewater treatment, and
antifouling properties. Meanwhile, the novel properties and excellent
performance of MoS2-based membranes are compared to other types of
Y. Liu et al.
2D-based membranes (mainly GO-based membranes). Finally, we will
highlight the future challenges and opportunities in order to realize the
full potential of MoS2-based membranes in water treatment and
purification.
2. Synthesis of MoS2 nanosheets
The MoS2 nanosheet is consisted of one sheet of molybdenum atoms
with two sheets of sulfur atoms, which is a sandwich structure.
Currently, there are two typical strategies to prepare 2D nanosheets
(including, but not limited to MoS2), which could be summarized in two
main methods: 1) the top-down methods, 2) the bottom-up methods.
The top-down methods mainly include mechanical, ultrasonic, liquid or
chemical peeling methods to cast off the weak van der Waals force be­
tween the layers. For the bottom-up methods, 2D nanosheets can be
obtained by directly growth using precursors. The major technical dif­
ficulty is how to assure the growth of 2D nanosheets in one direction and
simultaneously had small effect on the growth along the other two di­
rections. Although it is recently reported that the centimeter-scale MoS2
and GO nanosheets has been successfully prepared according to the
bottom-up synthesis strategy [6,32], the large production of high-
quality monolayer 2D nanosheets with large lateral size still remain
big challenge. We should combine the material properties and our goal
for the applications to choose the appropriate synthesis method to
fabricate the 2D nanomaterials.
Li-ion intercalation method was the most commonly used to fabri­
cate single-layered MoS2 nanosheets. Chemically exfoliated MoS2 (ce-
MoS2) nanosheets were often named with the synthesis method [48].
Ambrosi et al., [49] used three different lithium intercalation com­
pounds (including n-Bu-Li, t-Bu-Li and Me-Li) to exfoliate MoS2. Results
revealed that n-Bu-Li and t-Bu-Li were more effective intercalators to
fabricate ce-MoS2 than Me-Li, evidenced by the smaller size and fewer
layers of the nanosheets. When fabricating membranes, single layered
MoS2 hold the advantages of tuning membrane structure and properties
(e.g. membrane thickness, water transfer channel, hydrophilicity,
charge density, etc.). In addition, few layered MoS2 nanosheets were
also often used for membrane fabrication. With the assist of ultra-
sonication, bulk MoS2 powders in organic solvents can be exfoliated to
few-layered MoS2 (around 5–20 monolayers) [50]. Most recently, the
large-scale production of MoS2 nanosheets was achieved by using liquid
nitrogen. The obtained MoS2 nanosheets were pure and fewer than three
layers after the evaporation of liquid nitrogen [51]. In the bottom-up
methods, MoS2 nanosheets are synthesized using precursors contain­
ing Mo and S atoms such as hydrothermal reaction and chemical vapor
deposition (CVD). The method by using Mo- and S- precursors to
assemble Mo and S atoms was mature for fabricating MoS2 nanosheets
[52]. Among all the synthesis method, MoS2 nanosheets prepared by Li-
ion intercalation and sonication method were mostly used for fabri­
cating MoS2-based membranes. As for CVD method, MoS2 could be
obtained to fabricate membranes with no defect, thus expand it for
large-scale production. In addition, the modification of MoS2 during the
synthesis was simultaneously conducted and then was used for fabri­
cating high-performance membranes.
3. Types of MoS2-based membranes
3.1. Nanoporous MoS2 membranes
As well-known, graphene can be used to as an ultrathin separation
membrane (i.e., nanoporous graphene membrane) by drilling nanoscale
pores along the planar of graphene [6,53]. Therefore, similar ideas are
used to explore MoS2 membranes. As a typical graphene-like nano­
materials, a single layer of MoS2 also possesses high structural strength,
atomic-thickness, chemical and mechanical stability [13,18,54,55]. The
appropriate size of nanopores in monolayer MoS2 can be artificially
created, and the nanoporous membrane with efficient and low-energy-
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Chemical Engineering Journal 422 (2021) 130082
consumption are obtained for separating water and other components
(e.g. salts and pollutants). Notably, most studies of nanoporous MoS2
membranes focus on the desalination process since the nanopore size
approaches the diameter of the hydrated ions.
Molecular dynamic simulations were firstly used to realize the initial
demonstration of the potential for a single layer of MoS2 as water-related
separation membranes. Heiranian et al., [56] performed the molecular
dynamic simulations to highlight the possibility and prospect of using
nanoporous MoS2 membranes for water purification, they found that
>88% ions could be rejected by monolayer MoS2 with pore area ranging
from 20 to 60 A2, and the water flux was 70% better than the nano­
porous graphene under optimal conditions. Another study conducted by
Kou et al., [57], they also confirmed that nanoporous MoS2 membranes
had superior desalination performance via all-atom molecular dynamics
simulations. Moreover, they found that optimal nanopore diameter was
around 0.74 nm, the nanoporous MoS2 membranes showed excellent
water permeability and perfect salt rejections. Besides, Mi et al., suggests
that the nanopore size should be controlled in the range of 0.44–1.05 nm
in order to obtain optimal water flux and salt rejection [18].
Current studies on nanoporous MoS2 membranes focus on molecular
dynamic simulation, while the experimental studies are really lack.
Many research efforts on experimental techniques are being made to
verify the results of theoretical calculation and simulation. Liu et al.,
[58] successfully prepared nanoporous MoS2 membranes with 1–10 nm
diameters using a highly focused electron beam and transmission elec­
tron microscope, although this membrane was considered to be used for
DNA translocation rather than water-related membranes. Afterwards,
research on nanoporous MoS2 membranes was pushed forward by
Drndic et al., in 2018 via experimental results [59]. They created sub-
nanometer vacancies in suspended monolayer MoS2 by Ga+ ion irradi­
ation, nanoporous MoS2 membranes contained ~300 to 1200 pores and
the average and maximum diameters of these pores were ~0.5 and ~1
nm, respectively. The detailed description can be found in Fig. 2.
Furthermore, they revealed that pores with diameters less than 0.6 nm
were too small for ions to pass through, which was almost consistent
with the simulation results.
The separation mechanisms of this type membrane mainly involve
steric effects [56], the formation of single chain hydrogen bonds [57],
electrostatic repulsion between charged species and nanopores [15].
According to separation mechanisms, it could be inferred that the
membrane performance of nanoporous MoS2 membranes are mainly
dependent on pore characteristics (e.g. nanopore size and geometry,
pore density, atom type at the pore edge), filtrated species (e.g. hydrated
radius and valence state of ions), and applied external pressure. These
affecting factors have been investigated by molecular dynamic simula­
tion methods and experimental techniques. Monolayer MoS2 possesses
two types of atoms (i.e. Mo and S), which is different from graphene that
only containing carbon atom. This structure characteristics facilitates to
create different pore edges, thereby offering more flexibility and
tunability in designing nanoporous MoS2 membranes. The membrane
performance of Mo-only, S-only and Mo-S mixed with similar sizes were
compared, the nanoporous MoS2 membrane with Mo-only pores had the
largest water flux due to the hydrophobic edge, the fish-bone structure
and the conical geometry of Mo-only pore [56]. Köhler et al., also found
that the nanopore geometric and chemical characteristics played key
roles in water permeation [60]. Moreover, their study results suggested
the ion rejection were highly dependent on the cation charge. Besides,
the applied external pressure during the filtration greatly affected the
membrane permeability, for example, some research have demonstrated
that the water flux augmented linearly with the increasing applied
external pressure [57,61], which was likely attributed to larger energy
barrier of ions compared to that of water molecules in MoS2 pores.
From the summary of this section, theoretical calculation and
simulation studies have shown that both high salt rejection and rapid
water transport properties could be achieved with nanoporous MoS2
membranes, and thus most likely lead to the breakthrough of the trade-
Y. Liu et al.
Fig. 2. (a) aberration-corrected scanning transmission election microscopy characterization of five pore sizes and corresponding structure from molecular dynamics
simulations. (b) current cures and (c) conductance G panel of five pore sizes computed by molecular dynamics simulations [59].
off between permeability and selectivity. Pore characteristics, filtrated
species and applied external pressure greatly affect the membrane per­
formance. The large-scale and defect-free monolayered MoS2 and the
controlled generation of uniform pores on the planar are two important
challenges in the developments of nanoporous MoS2 membranes. The
fabrication of a large-scale and defect-free monolayer MoS2 represents a
first step towards the application of nanoporous MoS2 membranes. CVD
method may help to obtain monolayer with large-scale and defect-free
[13]. Besides, it has been reported that more mechanically stability of
monolayer MoS2 with high crystallinity could be realized by modified
CVD method [62]. To some extent, the large-scale preparation of
nanoporous MoS2 membrane is far from that of nanoporous graphene
membranes [13]. It should be noted that the Young’s modulus of
monolayer MoS2 is relatively lower than that of graphene [55], MoS2
monolayers are prone to be deformable for the formation of uniformly
distributed pores. Additionally, the controlled generation of pores in
monolayer MoS2 remains an important challenge, since current research
studies mostly focus on molecular dynamic simulations and experi­
mental studies are still lack. Some methods of producing nanopores in
graphene, such as oxygen plasma etching [53], electron beam radiation
[63] and helium ion beam [64], may provide certain reference for
creating pores in a single layer of MoS2.
3.2. Layer-stacked MoS2 membranes
The sheet-like structure and tunable physicochemical properties of
2D materials offer great opportunities to fabricate novel water-related
separation membranes with high performance by stacking 2D nano­
sheets. The capillary width (i.e. the free layer spacing) between 2D
nanosheets can realize efficient sieving of molecules and ions with
different sizes. Precise and optimal control of the free layer spacing
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Chemical Engineering Journal 422 (2021) 130082
enable to achieve both high selectivity and permeability. The layer-
stacked membranes fabricated by two-dimensional nanosheets could
allow the water molecules to go through the nanosheets in ultrafast
speed to achieve the goal of separation via nanochannels between the
layers. At present, pressure-assisted filtration with simple operation and
large-scale production is the most commonly used method for fabri­
cating layer-stacked MoS2 membranes. The main procedure for mem­
branes fabrication is as follows: a certain concentration of MoS2
nanosheets in dispersion is filtered on the substrates under applied
external pressure, leading to formation of stacked MoS2 layers with the
capillary width. The vacuum filtration method could be regarded as a
special case of the pressure-assisted filtration method.
3.2.1. The stability and separation mechanisms of layer-stacked MoS2
membranes
GO membranes, as the hottest studied layer-stacked membrane,
without any stabilization treatment could suffer from serious membrane
swelling in aqueous solution due to a large amount of oxygenated
functional groups in GO nanosheets [7]. In contrast, layer-stacked MoS2
membranes have shown high stability in aqueous solutions since com­
parable van der Waals and hydration forces could maintain the inter­
layer spacing of layer-stacked MoS2 membranes [15]. In other words,
MoS2 has larger Hamaker constant compared to GO, leading to the
stronger molecular interaction. The membrane stability has been paid
special attention in the development of MoS2-based membranes. Wang
et al., revealed that the swelling of the layer-stacked MoS2 membrane
did not occur over the 3 days of soaking in aqueous solution [15]. Longer
experiment of membrane stability was conducted in another study by
immersing MoS2 membrane with cation tunable interlayer in NaOH (pH
= 11) or HCl (pH = 1) solutions, the FO performance suggested the MoS2
membrane was sufficiently stable in aspect of permeability and rejection
Y. Liu et al.
[65]. Besides, the stability of multifunctional MoS2 membrane (inter­
calating Fe(OH)3 nanoparticles into stacked layers for efficiently
oxidizing contaminants) was evaluated, indicating the stable layer
structure under harsh working conditions [38].
It should be emphasized that the water molecular have an important
influence on the interlayer spacing of layer-stacked MoS2 membranes.
Stacking MoS2 in a dry state has an interlayer spacing of ~ 0.62 nm, it
means a free spacing of ~ 0.32 nm can be obtained by deducting the
thickness of Mo-S layers (~0.3 nm) [8,15]. However, current experi­
mental studies have shown that the free spacing of layer-stacked MoS2
membranes was much>0.30 nm in aqueous solutions, for example, the
free spacing values of ~ 0.64 nm [66], ~0.98 nm [15], ~1.14 nm [8],
~1.48 nm[67] and ~ 7.98 nm[67] were reported in layer-stacked MoS2
membranes. Obviously, such large interlayer spacing can allow both
salts and water molecular to pass through the layer-stacked membranes.
Even if the layer-stacked MoS2 membranes exhibited relatively high ion
rejection rates, the rejection mechanism was not dominated by size-
sieving effect from the free spacing of stacking MoS2 layers but for
other rejection mechanisms of interaction (e.g. electrostatic repulsion).
For both the fabrication of layer-stacked MoS2 membranes and their
application in water treatment and purification, the interactions be­
tween MoS2 nanosheets and water molecular should not be ignored,
which is directly associated with the interlayer spacing of MoS2 mem­
branes. Wang et al., discovered MoS2 membranes assembled via
pressure-assisted filtration almost entirely lost its water permeability
after oven-dried at 60 ◦ C for 2 h, the free spacing was changed from ~
0.9 nm to ~ 0.3 nm [15], as shown in Fig. 3a. Another study also
demonstrated the similar experimental results (Fig. 3b) [8]. Molecular
dynamics investigation has been conducted to try to explain this phe­
nomenon in few past years, and these theoretical investigations revealed
that water molecules could form a planar multi-layered structure
Fig. 3. Characterization of interlayer spacing in the layer-stacked MoS2 membranes. (a) from reference. [15] (i) XRD patterns during a drying and rewetting process.
(ii) the change of interlayer spacing of wet MoS2 and GO membranes with increasing time. (iii) the effects of free spacing on different force in MoS2 and GO
membranes. (b) from reference. [8] (i) XRD patterns of pristine and intercalated MoS2 membranes. (ii, iii) schematic illustration. (iv, v) TEM image. (vi, vii) SEM
cross-section images of pristine and intercalated MoS2 membranes.
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Chemical Engineering Journal 422 (2021) 130082
between two MoS2 layers [68-70], leading to the increasement of the
interlayer distance of stacking layers. Additionally, these findings
demonstrated water intercalation did not change the arrangement of S-
Mo atoms on the planar surface [68]. Therefore, it is suggested that
layer-stacked MoS2 membrane need to be kept in wet/hydrated condi­
tion or be rewetted using solvents (e.g. isopropanol) in order to maintain
enough large free spacing for the water transport.
Notably, one great advantage of 2D-based membranes is their
tunable structure to improve water flux and rejection of unwanted
species [14,71-73]. In theory, the free spacing of nanochannels in the
layer-stacked membranes can be precisely controlled by inserting some
species in order to achieve efficient and selective separation. Similar to
the design of GO membranes via cross-linking methods, the interlayer
spacing of the MoS2 membranes can be also tuned using different linking
agents to improve the rejection efficiency. Recently, Lu et al., [8]
fabricated layer-stacked MoS2 membrane by intercalating an amphi­
philic ligand as a cross-linker to tune the interlayer spacing, evaluating
the effect of the interlayer spacing on separation performance. Besides,
in order to improve water-salt selectivity, another strategy was to
functionalize the layer-stacked MoS2 membranes. For example, Hir­
unpinyopas et al., reported that the layered-stacked MoS2 membranes
were fabricated by the filtration method, and which were subsequently
functionalized by immersion in dye solutions [30]. The scheme is
illustrated in Fig. 4. The surface chemistry was changed due to the
charge of ions with functionalization of the dye, where minimal effect
occurred on its interlayer spacing.
3.2.2. The multifunctionality of layer-stacked MoS2 membranes
Currently, the combination of layer-stacked MoS2 membranes with
advanced oxidation process [38], photocatalytic and adsorption tech­
nologies [36,37,74] has been reported for improving membrane
Y. Liu et al. Chemical Engineering Journal 422 (2021) 130082

Fig. 4. (a) schematic illustration of Na+ and Cl- ions through dye-functionalized MoS2 membranes. (b) comparison of Na+ rejection of different MoS2 membranes (6
μm thick) [30].

performance, and/or alleviating membrane fouling and/or enhancing
the removal efficiencies of contaminants. MoS2 as one of extensively
studied transition metal dichalcogenide has been used for the photo­
catalytic hydrogen evolution reactions and the removal of environ­
mental contaminants due to its unique sulfur-rich characteristics, photo
electronic and optical properties and so forth [26,75-78]. A bandgap
value of MoS2 was increased within decreasing the number of layer,
there are two extreme cases: ~1.2 eV for bulk MoS2 and ~ 1.9 eV for a
single of MoS2 [48,79]. Moreover, the structural characteristics of MoS2
nanosheets (e.g. crystal phase, interlayer spacing and vacancy defect)
facilitate to tune membrane performance, and also offer a great promise
for combining with other water treatment process. The integration of
different water treatment processes can achieve efficient removal of
contaminants with energy-saving and cost-effective. The development
of multifunctional MoS2-based membranes has drawn increasing inter­
est in the area of water treatment and purification. Chen et al., designed
a layer-stacked MoS2 membranes with insertion of Fe(OH)3 nano­
particles to obtain a high water flux of 154 LMH/bar [38]. Interspacing
of MoS2 membranes were equivalent to the catalytic platform to enable
the reactive radicals with short longevity to efficiently oxidize con­
taminants. For example, durable degradation of Bisphenol A (>90%)
was achieved within the retention time of only 60.4 ms. High exposure

Fig. 5. Formation of atomic vacancies induced by sunlight irradiation. [36] (a, b) TEM images of pristine 1 T-MoS2 and atomic-defect-rich 1 T-MoS2. (c, d, e) HRTEM
images and simulations of three types of vacancy defects. (f, g, h, i) electron spin resonance spectra. (j) formation mechanism of vacancy defects.

6
Y. Liu et al.
of active surface and edges and the confined nanofluids in interlayer
spacing were responsible for the high membrane performance and the
efficient removal of Bisphenol A. Besides, the redox-reduction reactions
occurred on the surface of MoS2 membrane in order to recover precious
heavy metal [35,74], which will be discussed in detail in the part of
membrane application section. As for the combination of adsorption
process, Zhang et al. demonstrated the atomic-defect-rich 1 T phase was
produced by sunlight irradiation, and then which was used as blocks
building to fabricate layer-stacked MoS2 membranes (Fig. 5) [36]. The
defect-rich features were beneficial for the ion capture and water mo­
lecular permeation. This membrane exhibited high water flux of
181–345 LMH/bar and efficient removal Pb2+ efficiencies of
84.5–99.6%. Their research group also reported the layer-stacked MoS2
membranes consisting of pure 2H phase was fabricated under solar
illumination, applying for water desalination in solar thermal technol­
ogy. The superior water flux of 334–461 LMH/bar and excellent
chemical structural stability were obtained [37].
3.2.3. Summary of layer-stacked MoS2 membranes
Many research efforts were made to fabricate the layer-stacked MoS2
membranes via vacuum and pressure-assist filtration as the most
commonly used method. The assembly of the layer-stacked MoS2
membranes are facile, environmentally-friendly and achievable on a
large scale. The layer-stacked MoS2 membranes without tunability
exhibited strong stability, high water flux and rejection of large mo­
lecular, which may be efficient for molecular separations from aqueous
solutions but not suitable for desalination application. In order to ach­
ieve high selectivity and permeability of ions, the tunability and control
of interlayer spacing were conducted. The control of interlayer spacing
reported mainly depends on covalent bonds and electrostatic forces. To
adjust the distance between the layers, MoS2 could be modified ac­
cording to the physicochemical properties of the nanomaterial and the
membrane fabrication parameters to control the membrane structure
and properties. The materials can be added with special properties, such
as amphiphilic molecules and nanoparticles, in the process of membrane
fabrication to adjust the distance between layers. The operation pa­
rameters including filtration pressure and speed also could affect the
distance between MoS2 nanosheets, the orientations of nanosheets
(parallel alignment or micro-domains) and membrane thickness.
Therefore, filtration parameters in the fabrication process need to be
paid attention for the adjustment and optimization of the interlayer
spacing. In particular, the unique structural characteristics and physi­
cochemical properties of MoS2 nanosheets facilitate the preparation of
multifunctional membranes. It should be emphasized that the structural
characteristics of layer-stacked membranes such as crystal phase,
interlayer spacing and vacancy defect can offer a great promise for
combining membrane process with other water treatment technology
such as advanced oxidation process, photocatalytic and adsorption
technologies. The increased requirement of effective and energy-
efficient treatment process in water treatment and purification will
accelerate the exploration of novel multifunctional MoS2-based mem­
branes in the future studies.
3.3. The MoS2 composite membranes
3.3.1. MoS2-incorporated composite membranes
Currently, most used commercial membranes including porous and
dense membranes are made from various polymers such as poly(vinyl­
idene fluoride) (PVDF), polysulfone (PSF), polyacrylonitrile (PAN), poly
(ether imide) (PEI) and polyethersulfone (PES) and so forth. Polymeric
membranes still represent the state-of-the-art of membrane-based sep­
aration in water treatment and purification mainly due to processability
on large scale and operating conditions for stability, simplicity and cost-
effectiveness [1,2,16]. The integration of MoS2 nanosheets in the design
of polymeric membranes offer great potential for improving membranes
mechanical and thermal stability, permeability and selectivity as well as
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Chemical Engineering Journal 422 (2021) 130082
reducing membrane fouling propensity [40,47,80-82]. Most research
work focus on incorporating MoS2 nanosheets into the organic phase,
and then the mixture could be casted together to fabricate MoS2-inco­
porated composite membranes with high membrane performance. There
are two strategies for preparing MoS2- incorporated composite mem­
branes: one strategy is that MoS2 nanosheets are directly mixed into
polymeric solutions; the other one is that MoS2 nanosheets are pre-
functionalized prior to the incorporation of the polymer matrix, fol­
lowed by phase inversion for fabricating separation membranes.
The excellent properties of MoS2 nanosheets, including the negative
charge, laminate structure and hydrophilic sites and so forth, can be
used to enhance the membrane performance of porous polymeric
membranes, these membranes are mainly used for microfiltration (MF)
and ultrafiltration (UF) processes. Using MoS2 nanosheets as an additive,
Saraswathi et al., investigated the effect of MoS2 content on hydrophi­
licity, surface morphology and antifouling properties of the composite
PVDF membranes [40]. They found that incorporating MoS2 nanosheets
at 0.5 wt% directly into the polymeric solutions could obtain optimal
membrane performance in terms of pure water flux, water content,
porosity, bovine serum albumin (BSA) rejection. The similar results were
obtained in another study, in which three different MoS2 concentrations
(0.5, 1 and 2 wt%) were mixed with PEI to fabricate the composite
membranes. In addition, the antifouling and antibacterial properties of
the MoS2/PES membranes were enhanced. Overall, in the design of the
MoS2-incorparated composite membranes, it could be inferred that two
key factors should be given special attention. One is that the adding
content of MoS2 was relatively low (mostly controlled less than 1 wt%),
the other is that the mixed solution was homogeneous. The control of
two key factors enables it to guarantee the integrity of the polymeric
membrane, on the other hand, to take full advantage of the excellent
properties of MoS2.
The thin film composite (TFC) membranes comprise a non-porous,
highly crosslinked polyamide and/or polyimide (PA) selectivity layer
and a porous polymer substate [9], which are widely used for nano­
fltration (NF), reverse osmosis (RO) and forward osmosis (FO) processes
in water treatment and purification. Interfacial polymerization typically
involves the preparation of the PA selectivity layer [9]. During the
fabrication process, MoS2 nanosheets can be employed as an additive for
construction of thin film composite membranes. Li et al., successfully
prepared a novel thin film nanocomposite (TFN) RO membrane by
incorporating of MoS2 nanosheets into PA matrix through interfacial
polymerization of m-phenylenediamine (MPD) and trimesoyl chloride
(TMC) monomers [83]. The MoS2-TFN membrane at 0.01 wt% exhibited
high permeability-selectivity (6.2 LMH/bar of water flux and 98.6% of
salt rejection) and superior antifouling properties (91% of the normal­
ized water flux). The enhanced membrane performance was attributed
to the negative charge and the hydrophilic sites of layered MoS2. The
scheme of membrane fabrication and rejection mechanism are illus­
trated in Fig. 6.
Another strategy for fabricating MoS2- incoporated composite
membranes is that MoS2 nanosheets are functionalized and followed by
inclusion in the polymer solutions, which is used to fabricate the com­
posite membranes embedded with functionalized MoS2 nanosheets via
the phase inversion. Even if MoS2 nanosheets are relatively inert [84],
some attempts have been made to modify MoS2 nanosheets during the
synthesis process of monolayer and few-layer MoS2. For example, in
order to further improve the hydrophilicity and other function of poly­
meric membranes, the mixture of MoS2 nanosheets and zwitterions into
the PES membranes was conducted [33]. Amphoteric polymer was
firstly grafted onto the layer surface of MoS2 in the process of exfoliation
of MoS2 bulk, which were then blended into the casting solution to
fabricate the composite membranes with zwitterionic functionalized
MoS2 nanosheets via phase inversion. The preparation process is pre­
sented in Fig. 7a. The composite membranes showed high water flux
(108.3 L⋅m− 2⋅h− 1 at 6 bar), dye retention (98.2% for Reactive Black 5%
and 99.3% for Reactive Green 19) and low salt rejection (less than 2.2%
Y. Liu et al.
Fig. 6. Fe 6. schematic illustration of MoS2-TFN membrane fabrication and rejection mechanism [83].
Fig. 7. Schematic illustration of fabrication of the composite membranes embedded with functionalized MoS2 nanosheets. (a) the MoS2-PSBMA/PES composite
membrane[33]. (b) the TA-MoS2-TFN membrane [85].
for Na2SO4, MgCl2, NaCl and Mg2SO4). As for the dense polymeric
membranes modification of functionalized MoS2 nanosheets, it was re­
ported that tannic acid (TA) was firstly used to modify MoS2 nanosheets
during the exfoliation of bulk MoS2, and then TA-MoS2 nanosheets were
employed as an additive to form the PA layers via typical interfacial
polymerization of piperazine (PIP) and TMC monomers [85]. The syn­
thesis process of the thin film nanocomposite membranes is described in
Fig. 7b. The reaction of TA and TMC enabled the MoS2 nanosheets were
covalently linked into the PA layers for enhancing homogeneousness
and compatibility between MoS2 nanosheets and the polyamide matrix.
The composite membrane exhibited high permeation of 17.0 LMH/bar
and the salt rejection of 98.5%.
3.3.2. Membrane surface modification with MoS2 nanosheets
To improve membranes performance, the commonly used approach
is to coat some nanomaterials onto the surface of established commer­
cial membranes. Layer-by-layer (LbL) assembly method provides precise
control of the nanomaterials loading on the membrane surface, which
typically involves the alternative deposition of two materials via
attractive forces such as electrostatic attraction and van der Waals force
[14,86]. Previous studies on the surface modification using GO nano­
sheets have demonstrated the enhanced membrane properties such as
antimicrobial effect and chlorine resistance [87,88]. The oxygen func­
tional groups facilitate GO nanosheets to be coated on the surface of
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Chemical Engineering Journal 422 (2021) 130082
polymeric membranes [89,90]. Unlike GO nanosheets, making MoS2
nanosheets adhere to the surface of polymeric membranes remains a
challenge since MoS2 nanosheets do not possess functional groups for
easily reacting with polymers.
However, some attempts have been made to employ MoS2 nano­
sheets to modify the membrane surface via LbL assembly. In one study
conducted by Zhou et al., [31], the modified MoS2 nanosheets via poly
(diallyldimethylammonium chloride) (PDDA) as a positively charged
polycation, and poly(sodium 4-styrenesulfonate) (PSS) as a negatively
charged polyanion were sequentially deposited onto the poly­
acrylonitrile substrate to assemble MoS2/polyelectrolytes hybrid mem­
branes. The LbL assembly process is described in Fig. 8a. The assembled
(PDDA@MoS2-PDDA/PSS)4.0 hybrid membrane achieved better NF
performance. Liu et al., reported that the MoS2 nanosheets were firstly
modified using polydopamine (PDA) and then MoS2@PDA was depos­
ited on the hydrolyzed PAN membranes to prepare MoS2@PDA NF
membranes with high water flux (204.05 LMH/bar) and methylene blue
rejection (99%)[91]. This research group also coated poly (sulfobetaine
methacrylate) (PSBMA) on the surface of the MoS2 membrane via a
simple PDA-assisted one-step codeposition to prepare PSBMA/PDA/
MoS2 NF membranes in order to improve membrane performance (i.e.
the water flux of 262 LMH/bar and methylene blue rejection of 99.8%)
[92].
As for the surface modification of the dense polymeric membranes by
Y. Liu et al.
Fig. 8. Surface modification by MoS2 nanosheets. (a) MoS2/polyelectrolytes hybrid NF membranes. [31] (b) MoS2-coated-FO membrane. [47] (c) MoS2/PEI
composite membrane [80].
MoS2 nanosheets, the LbL assembly method was also adopted. Li et al.,
immersed the base PES FO membrane in a dopamine solution, followed
by poly (ethyleneimine) solution and MoS2 dispersion, and finally poly
(acrylic acid) solution [47]. Such LbL deposition resulted in the forma­
tion of a tri-layer FO membrane. The schematic illustration of fabrica­
tion information is provided in Fig. 8b. The MoS2-coated-FO membrane
exhibited high water flux of 27.15 L⋅m− 2⋅h− 1, low salt reverse flux of
16.42 gMH and excellent antifouling ability. Apart from the most
commonly used commercial polymeric membranes, recent studies were
conducted to coat MoS2 nanosheets onto the surface of ceramic mem­
branes [80,93]. It was reported that the fabrication of a positively
charged MoS2 composite membrane on a ceramic hollow fiber (CHF),
polyethyleneimine was used to enhance the interfacial adhesion be­
tween MoS2 nanosheets [80]. Fig. 8c describes that the construction of
MoS2/ polyethyleneimine composite membrane. The resulting mem­
brane displayed an excellent desalination performance, i.e. a pure water
flux of 4.6 LMH/bar and MgCl2 rejection of 95.5%.
3.3.3. Summary of MoS2 composite membranes
Polymeric membranes still represent the state-of-the-art of
membrane-based separation in water treatment and purification. The
MoS2 composite membranes could take advantage of the negative charge
and the hydrophilic sites of MoS2 nanosheets is to improve flux perme­
ability, selectivity and antifouling properties. The design and fabrication
of MoS2-incorporated and MoS2-surface modification membranes are
mostly based on these polymeric membranes. In other words, incorpo­
rating of MoS2 into the organic phase as casting solutions and loading
MoS2 on the surface of polymeric membranes are employed to enhance
the membrane performance of porous and dense polymeric membranes
using the fascinating properties of MoS2 nanosheets or pre-functionalized
MoS2 nanosheets. During the fabrication process, the mixture of MoS2
nanosheets and polymer solutions should be homogeneous. In addition,
LbL assembly method is commonly used to provide precise control of the
nanomaterials loading on the membrane surface modification. The
combination of MoS2 nanosheets and commercial UF/NF/RO membranes
has received much attention for desalination, the removal of some con­
taminants (e.g. heavy metals, microorganic pollutants and oils), which
will be discussed in detail in the application parts.
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Chemical Engineering Journal 422 (2021) 130082
4. Application of MoS2-based membranes
There exists various kinds of synthetic contaminants and natural
constituents in municipal and industrial wastewater, and surface water
such as rivers, lakes, oceans and wetlands [16,94-98]. Membrane tech­
nique has demonstrated a viable and powerful tool to produce clean
water by removing various unwanted species. Aiming at the practical
application of membrane process for the treatment and purification of
water, it is more promising to discuss the fabrication and design of MoS2-
based membranes. This part placed the emphases on summarizing
recent developments and application of MoS2-based membranes based
on various kinds of water contaminants (or unwanted species) removal
from the perspective of desalination, industrial wastewater treatment
and antifouling properties.
4.1. Desalination
It was reported in 2016 that global desalination plants had the total
capacity of 88.9 million m3/d (nearly 95.6 million of contract capacity)
for producing the fresh water [13,54]. Membrane separation process can
play a key role in desalination. The two indicators including the water
flux and salt rejection are mainly used to assess the effectiveness and
performance of desalination membranes. Exploring more efficient and
low-energy-consumption of desalination membranes is urgently needed
to perfect the desalination process. In recent years, 2D-based mem­
branes have been extensively studied for more efficient desalination
process. MoS2 is regarded as a typical graphene-like nanosheets, thus the
MoS2-based and graphene-based membranes are often compared in
aspect of membrane fabrication and membrane performance. The
detailed discussion of these two types 2D-based membrane will be given
in the lateral part. As for MOF/COF membranes for desalination, it
seems that porous MOF/COF membranes would possess some advan­
tages compared to graphene/MoS2 membranes (i.e. porous and layer-
stacked membranes) because of shorter transport pathways [24].
However, most MOF nanosheets are insufficient in aqueous solution
except for a few types of MOFs (e.g. MIL, UiO-66, and ZIF series [99]).
Currently, there are a few reported examples to directly apply MOF
membranes in desalination. The pore size of reported porous COF
Y. Liu et al.
Table 1
The summary of MoS2-based membranes for desalination.
Membrane Types Fabrication Methods
Nanoporous MoS2 Molecular dynamics simulations
Membranes
Molecular dynamics simulations
MoS2 nanosheets preparation: CVD growth
Layer-stacked MoS2 MoS2 nanosheets preparation: solvent assisted liquid exfoliation;
Membranes functionalized laminar MoS2 membranes fabrication: filtration method
and sunset yellow (SY) was used to functionalize the laminar
membranes.
MoS2 nanosheets preparation: chemical exfoliation (lithium
intercalation); membranes fabrication: pressure-assisted filtration
Modified MoS2 nanosheets preparation: a tannic acid (TA) assisted
liquid exfoliation method; TA-modified MoS2 membranes fabrication:
vacuum filtration
Functionalized MoS2 nanosheets: chemical liquid (lithium intercalation)
and then functionalized by organohalide reagents; MoS2 membranes
fabrication: vacuum filtration
MoS2 nanosheets preparation: solvent assisted liquid exfoliation; MoS2/
GO membranes fabrication: vacuum filtration by mixing GO and MoS2
nanosheets solutions
Nanoporous MoS2 nanosheets preparation: solvent assisted liquid
exfoliation and intrasheet pore diameter was tuned by cavitation
method
MoS2-incorporated MoS2 nanosheets preparation: solvent assisted liquid exfoliation; MoS2-
Composite Membranes TFN RO membranes fabrication: interfacial polymerization
TA functionalized MoS2 nanosheets preparation: TA assisted liquid
exfoliation
MoS2 nanosheets preparation: solvent assisted liquid exfoliation; MoS2
nanosheets modified TFC membranes fabrication: interfacial
polymerization
O-MoS2 nanosheets preparation: the Hummers’ method; O-MoS2 NF
membrane fabrication: interfacial polymerization
Membrane Surface MoS2 nanosheets: purposed from XFNANO; MoS2-coated-FO membrane
Modification with fabrication: LbL deposition
MoS2 Nanosheets
Poly (diallyldimethylammonium chlo- ride) (PDDA) modified MoS2
nanosheets preparation: hydrothermal method; PDDA@MoS2 hybrid
membranes fabrication: LbL self-assembly
MoS2 nanosheets preparation: solvent assisted liquid exfoliation; MoS2
composite membranes fabrication: the mixture of positively charged
MoS2 composite membrane on a ceramic hollow fiber and MoS2 was
stacked on TiO2-coated ceramic hollow fiber by filtration and dried.
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Chemical Engineering Journal 422 (2021) 130082
Membrane Key Feature and Performance Reference
Ions rejection: > 88%; water flux: ~70% greater than [56]
graphene nanopores when the pore areas ranged from 20 to 60
Å2
Salt rejection: 100%; permeability: 4.27 L/cm2⋅d⋅MPa under [57]
optimal conditions of pore diameter of 0.74 nm and a low
pressure of 4.8 bar
Rejections of various seawater salts including Na+, K+, Ca2+ [32]
and Mg2+: >99%; pure water flux: >322 LMH/bar;
experimental conditions: static diffusion mode; membrane
thickness: ~0.7 nm; initial concentration: NaCl for 0.469 M,
CaCl2 for 0.1 M, KCl for 0.1 M, MgCl2 for 0.1 M
Salt rejection: ~99%; permeability: 0.033 LMH/bar; [30]
experimental conditions: NaCl feed concentration: 0.1 M;
MoS2/SY membrane thickness: 5 μm
Rejection of sodium-based ionic species (acetate, sulfate and [15]
citrate): ~55-70%; pure water flux: 50 LMH/bar; experimental
conditions: membrane thickness: 500 nm; ionic strength: less
than 2 mM; operation pressure: 4.1 bar
Rejections of various cations including K+, Na+, Li+, Ca2+ and [116]
Mg2+: 97%; water flux: 32 LMH; experimental conditions:
static diffusion mode, feed solution: DI water; draw solution:
0.25 M cation solution; the hybrid membrane: 5 µm-thick 1 wt
% TA-MoS2
NaCl rejection: 87%; permeability: 1.6 LMH/bar; experimental [108]
conditions: 500-nm-thick ethyl-2-ol- functionalized MoS2
membrane; operation pressure: 9 bar; initial concentration:
0.58 wt%
Rejections of salts : 96.85% for K3Fe(CN)6 , 66.76% for [106]
Na2SO4, 58.31% for MgSO4, 56.02% for NaCl and 44.85% for
MgCl2; pure water flux: 48.27 LMH/bar; experimental
conditions: GO/MoS2 composite membrane: 0.9 mL MoS2, 1
mL GO (0.1 mg/mL) and 100 mL DI water membrane;
operation pressure: 0.9 bar; initial concentration: 1000 mg/L
NaCl rejection: >95%; water permeability: 5 LMH; [46]
experimental conditions: FO mode, ~1-μm-thick membranes
with interlayer spacing of 7.8 ± 1.6 Å; initial concentration:
0.5 M
NaCl rejection: 98.6%, water permeability: 6.2 LMH/bar; [83]
experimental conditions: at MoS2 at 0.01 wt% for MoS2-TFN
membrane; operation pressure: 15.5 bar; initial concentration:
2000 mg/L
Na2SO4 rejection: 98.5%; permeability flux: 17 LMH/bar; [85]
experimental conditions: TA-MoS2 at 0.025 wt% for the
composite membrane; operation pressure: 6 bar; initial
concentration: 1000 mg/L
Na2SO4 rejection: 94.4%; pure water flux: 7.8 LMH/bar; [34]
experimental conditions: MoS2 at 0.010 wt/v% for the TFC
membrane; operation pressure: 3.5 bar; initial concentration:
2000 mg/L
Rejections of Na2SO4, MgSO4, MgCl2 and NaCl: 97.9%, 92.9% [103]
and 86.3%; pure water flux: 7.91 LMH/bar; experimental
conditions: O-MoS2 at 0.010 wt/v% for the composite
membrane; operation pressure: 3.5 bar; initial concentration of
salts: 2000 mg/L
Reverse flux of NaCl ions: 16.42 gMH; water flux: 27.15 LMH; [47]
experimental conditions: FO mode, feed solution: DI water;
draw solution: 1 M NaCl.
Rejections of Na2SO4, MgSO4, NaCl and MgCl2: 81.6%, 51.5%, [31]
27.9% and 16.1%; permeability: approximately 16 LHM/bar
experimental conditions: deposition cycles: 4; hybrid
membranes; operation pressure: 4 bar; salt solutions
concentration: 1000 mg/L
MgCl2 rejection: 95.5%; water permeability: 4.6 LMH/bar; [80]
experimental conditions: MoS2 loading of 0.133 /cm2;
operation pressure: 6 bar; initial concentration: 0.01 M
Y. Liu et al.
membranes (generally in the range of 0.64–5.8 nm) is too large to reject
salts in aqueous solution [100,101] and thus need to use effective stra­
tegies to reduce pore size if applying for desalination. MoS2 nanosheets
with sub-nanopores and layer-stacked MoS2 membranes with the nar­
rowed free spacing as the free-standing membranes have showed great
promise in desalination application. The integration of MoS2 nanosheets
with the commercial UF/NF/RO membranes, i.e. MoS2-incorated
membranes and MoS2 surface-modification membranes, have been
investigated to improve the desalination performance. It should be
emphasized that the current study of desalination membranes mostly
focuses on combing MoS2 nanosheets and commercial UF/NF/RO
membranes mainly due to stability, facility, efficiency and scalability of
these membranes. In this section, we will summarize and analyze the
performance and rejection mechanism of MoS2-based membrane which
applying for desalination process in terms of different valence salt so­
lutions. Table 1 presents MoS2-based membranes types, and related
fabrication and the desalination performance. The detailed information
on the membrane fabrication can be found in the previous section. We
hope to provide guidance of membrane design and selection according
to the requirement of salt rejections.
The primary desalination mechanisms mainly involve size exclusion
and electrostatic repulsion for the MoS2-based membranes including
nanoprous membranes, layer-stacked membranes, MoS2-incorporated
composite membranes and membranes surface modification with MoS2
nanosheets. Other interactions (e.g. the formation of single chain
hydrogen) also have some influence on the rejection efficiency. The
separation mechanisms are different from other 2D-based membranes
(e.g. GO, COF, MOF membranes), which also includes cation-π, π-π in­
teractions and/or coordination interaction [1,24,102]. As stated earlier,
the pore size, types and chemistry can play key roles in desalination
performance of the nanoporous MoS2 membrane. Especially, there may
exist critical pore size of 0.55–0.60 nm in diameter for the passage of
water molecules [54]. As for layer-stacked membranes, the salt rejection
is significantly dependent on the free spacing between MoS2 layers, it is
noting that the precise design of interlayer spacing should be conducted
for narrowing the nanochannels because layer-stacked MoS2 membranes
without tunability have relatively large spacing distance to allow
various ions to pass through. As for MoS2-incoprated membranes and
MoS2 surface-modification membranes, taking advantage of the nega­
tive charge and the hydrophilic sites of MoS2 nanosheets is to improve
flux permeability and selectivity of composite membranes.
The major goal of low-pressure operation without sacrificing salt
rejection are being pursued considering the energy consumption and
operation convenience. It is expected to achieve efficient rejection of
salts by using NF membranes. Researchers have made some efforts to
Fig. 9. Ions rejection mechanism and membrane performance. [46] (a) schematic illustration of the sub-nm pathways of water through the porous MoS2 membrane.
(b) comparison of membrane performance between the commercial SW30-HR and porous MoS2 membrane.
11
Chemical Engineering Journal 422 (2021) 130082
enable NF membrane with modification using MoS2 nanosheets to
obtain high selectivity and permeability. Yang et al., reported the MoS2-
based membrane with a typical negatively charged NF membrane dis­
played the highest rejection of Na2SO4 (~94%) and lowest rejection of
NaCl (~60%) [34]. This research group found that the introduction of
oxidized MoS2 nanosheets into the PA selective layer in the NF mem­
brane further enhanced the salt rejection [103], the rejections of
Na2SO4, MgSO4, MgCl2 and NaCl were respectively 97.9%, 92.9%,
86.3% and 65.1%, when the concentration of each salt was 2000 mg/L
at 3.5 bar and 25 ◦ C. The order of rejection rate was agreed with pre­
vious reports with typical negatively charged NF membranes [104,105].
Another study also showed the similar results, the negatively charged
MoS2-based membrane exhibited the highest rejection of 98.5% for
Na2SO4 among various salts [85]. The positively charged NF membranes
also could be fabricated by loading MoS2 nanosheets and polymers to
improve the rejection of multivalent cations, for example, the MoS2/
polyethyleneimine composite NF membrane achieved an excellent
desalination performance [80], i.e., a pure water permeance of 4.6
LMH/bar and high MgCl2 rejection of 95.5% when the trans-membrane
pressure was 6 bar and initial concentration of MgCl2 was 0.01 M.
During the desalination process, the Donnon theory played an import
role in both the negatively and positively MoS2-based NF membranes, i.
e. the charge was repelled by electrostatic repulsion and the counter ions
were also retained to maintain electrical neutrality [106,107], which
could help to explain the order of rejection rates for multivalent salts.
As for the rejection of mono-salt (NaCl), efficient separation of NaCl
in aqueous solutions using NF membrane remains big challenge, it is
necessary to operate under RO membrane module. As mentioned earlier,
the nanoporous MoS2 membranes were generally designed for desali­
nation process, while the layer-stacked MoS2 membranes without
tunability were not able to efficiently reject ions. Interestingly, a recent
study combined the unique characteristics of the two types of mem­
branes to fabricate a novel high-performance membrane[46], i.e. the
composite layer-stacked MoS2 membranes were made from the stacked
heterodimensional one- to two-layer-thick porous nanosheets and
nanodisks, as illustrated in Fig. 9. The experimental results showed 99%
of rejection of NaCl at initial concentration of 0.5 M under the optimal
condition. The excellent membrane performance was attributed to the
multimodal porous network structure with tunable surface charge, pore
size and interlayer. One study reported that the MoS2-based membranes
based on covalently functionalized had high rejection of ~ 87% when
the operation pressure was 9 bar using a 0.58 wt% NaCl solution [108].
The fabricated composite membrane consisting of GO, MoS2 nanosheets
and polyvinyl alcohol was employed for NaCl rejection, which showed
89% of rejection rate and 3.96 LMH of water flux at low pressure of 5 bar
Y. Liu et al. Chemical Engineering Journal 422 (2021) 130082

when using 2000 mg/L NaCl [109]. Besides, it was reported that the RO
membrane with loading 0.01 wt% MoS2 into PA matrix achieved the
optimal water permeability of 6.2 LMH/bar and salt rejection of 98.6%
measured at the 2000 mg/L NaCl solution at 15.5 bar and 25 ◦ C [83].
Especially, in a recent study, the actual seawater from the Atlantic coast
was tested to evaluate the desalination performance of the CVD grown
MoS2 membrane with near atomic thickness, nearly rejection rates of
100% was obtained, which outperformed conventional desalination
membranes [32]. Moreover, this research work produced centimeter-
scale MoS2 membranes with high performance, providing a great po­
tential for testing membranes in a bench-scale membrane system.
4.2. Industrial wastewater treatment
4.2.1. Dye separation
The dyes industry can consume large amount of clean water, and
discharge substantial amount of wastewater (~10.25% of the total liters
of industrial wastewater) containing inorganic salts and dyes [110],
which are insufficient to be treated by traditional biological process
because the high salinity could inherent microbial activity and these
dyes are also difficult to be degraded [33,111]. Currently, NF mem­
branes have been widely applied for the removal or recover of dyes from
wastewater [112,113]. More importantly, dyes are commonly used to
assess the separation performance of emerging membranes in a lab-scale
membrane system [8,15,114,115]. Therefore, it is very necessary for
sorting out the literature of the separation of dyes using MoS2-based
membranes. The membrane types, fabrication and membrane perfor­
mance of MoS2-based membrane applied for the rejection of dyes are
presented in Table 2.
Obviously, there are few reports on the nanoporous MoS2 mem­
branes for the separation of dyes from aqueous solutions, while two
other types of MoS2-based membrane including layer-stacked mem­
branes and MoS2 composite membranes were used to reject various
dyes. The layer-stacked MoS2 membranes without tunability could show
high water permeability and dye rejection, Sun et al., firstly reported
89% of rejection rate for evans blue with a water permeability of 245
LMH/bar using the layer-stacked membranes [29]. Wang et al., also
evaluated layer-stacked MoS2 membranes performance using dyes as

Table 2
The summary of MoS2-based membranes for dye rejection.
Membrane Types Fabrication Methods Membrane Key Feature and performance Reference

Layer-stacked MoS2 MoS2 nanosheets preparation: chemical exfoliation; membranes
Membranes fabrication: vacuum filtration
MoS2 nanosheets preparation: chemical exfoliation; membranes
fabrication: pressure-assisted filtration
MoS2 nanosheets preparation: liquid-based ultrasonic exfoliation;
MoS2/GO membranes fabrication: pressure-assist assembled method by
mixing GO and MoS2 nanosheets dispersion
MoS2 nanosheets preparation: solvent assisted liquid exfoliation; MoS2/
GO membranes fabrication: vacuum filtration by mixing GO and MoS2
nanosheets solutions
MoS2 nanosheets preparation: mixed-solvent mechanical exfoliation;
polydopamine-Modified MoS2 membranes fabrication: pressure-assisted
filtration and surface coating by polydopamine
Modified MoS2 nanosheets preparation: a tannic acid (TA) assisted
liquid exfoliation method; TA-modified MoS2 membranes fabrication:
vacuum filtration
Nanoporous MoS2 nanosheets preparation: solvent assisted liquid
exfoliation and intrasheet pore diameter was tuned by cavitation
method
MoS2-incorporated MoS2 nanosheets preparation: hydrothermal self-assembly; MoS2/PES
Composite Membranes composite membranes fabrication: a non-solvent induced phase
separation
Modified MoS2 nanosheets preparation: ultrasonic solvent assisted
liquid exfoliation and modified by zwitterionic 2-methacryloyloxy ethyl
dimethyl (3-sulfopropyl)-ammonium hydroxide sulfobetaine
methacrylate (PSBMA) using reverse atom transfer radical
polymerization method MoS2-PSBMA/PES composite membranes
fabrication: conventional phase inversion
Membrane Surface Poly (diallyldimethylammonium chlo- ride) (PDDA) modified MoS2
Modification with nanosheets preparation: hydrothermal method; PDDA@MoS2 hybrid
MoS2 Nanosheets membranes fabrication: LbL self-assembly
Evans blue rejection: 89%; permeability: 245 LMH/bar; [29]
experimental conditions: 1.7 µm of membrane thickness with
channel size of 3 nm; operation pressure: 1 bar; initial
concentration: 15 µM
Rhodamine-WT rejection: 89%; methylene blue rejection: [15]
initially 100% but decreased to a stable level of ~40%;
experimental conditions: 500 nm of membrane thickness with
interlayer spacing of 1.2 nm;
Methylene blue rejection: 97.4%; permeability: 7.65 LMH; [112]
experimental conditions: GO/MoS2 composite membrane: 10
mL GO solution (0.05 mg/mL) and 3 mL MoS2 solution;
operation pressure: 2 bar; initial concentration: 10 mg/L
Direct red 80 rejection: 99.99%; congo red rejection: 99.90%; [106]
rhodamine B: 99.79%; methylene blue: 99.66%; pure water
flux: 48.27 LMH/bar; experimental conditions: GO/MoS2
composite membrane: 0.9 mL MoS2, 1 mL GO (0.1 mg/mL) and
100 mL DI water membrane; operation pressure: 0.9 bar;
initial concentration: 20 mg/L
Methylene blue rejection: 100%; pure water flux: 135.3 LMH/ [117]
bar; experimental conditions: MoS2 loading of 0.1103 mg/cm2
at 4 h polydopamine-modification; operation pressure: 1 bar
Rejections of basic blue, toluidine blue and rhodamine 6 g: [116]
nearly 99.87 ± 0.1%; permeability: 15,000 ± 100 LMH/bar;
experimental conditions: the hybrid membrane: 5 µm-thick 1%
TAMoS2; operation pressure: 0.7 bar; initial concentration: 0.1
mg/mL
Rejections of rhodamine B and methylene blue: nearly 100%; [46]
methyl red rejection: approximate 80%; methyl orange
rejection: 90%; pure water flux: 232 ± 8.92 LMH/bar;
experimental conditions: ~1-μm-thick membranes with
interlayer spacing of 7.8 ± 1.6 Å; operation pressure: 1 bar
Rejections of acid yellow 14, eriochrome blue black R, methyl [81]
blue, evans blue, congo red, derect red 80: 13.0%, 70.6%,
80.6%, 97.8%, 96.2%, 98.7% ,99.9%; pure water flux: 286
LMH/bar; experimental conditions: MoS2 at 0.4 wt% for
composite MoS2/PES composite membranes; operational
pressure: 4 bar; initial concentration: 50 mg/L
Rejections of reactive Black 5 and reactive green 19: 98.2% [33]
and 99.3%; pure water flux: 18.05 LMH/bar; experimental
conditions: PSBMA-modified MoS2 at 1.0 wt% for the
composite membranes; operation pressure: 4 bar; initial
concentration: 500 mg/L
Methyl blue rejection: 98.6%; permeability: 19.45 LMH/bar; [31]
experimental conditions: deposition cycles: 4; hybrid
membranes; operation pressure: 4 bar; initial concentration:
200 mg/L

12
Y. Liu et al.
surrogates [15], the 500 nm thick membrane showed 90% of the
removal efficiency for rhodamine-WT, but the removal efficiency of
methylene blue decreased from initially 100% to ~40% due to mem­
brane adsorption at the beginning of filtration test. Size exclusion and
electrostatic repulsion are mainly responsible for the dye rejection using
MoS2 membranes, which was shown in Fig. 10. Some attempts of tuning
the interlayer spacing have been made to improve the removal of dyes
and permeability flux, for example, TA modified MoS2 nanosheet
membranes [116], PDA-modified layer-stacked MoS2 membranes[117],
the use of cations (K+, Na+, Li+ or Mg2+) intercalation [65] and the
mixture of GO and MoS2 nanosheets for enhancing the interlayer sta­
bilizing force [106,112]. The modification of the commercial mem­
branes surface by MoS2 nanosheets was conducted via LbL deposition
method [31,93]. Besides, the incorporation of MoS2 into polymetric
membranes was also reported to enhance dyes separation performance.
The detailed information of fabrication methods, operation conditions
and membrane performance could be found in Table 2. Moreover,
Table 2 shows the removal efficiency of dyes reached above 95% even
approaching ~ 100%, and the range of water flux were 100–200 LMH/
bar when the operation pressure was relatively low (i.e. 1–4 bar). Unlike
COF/MOF membranes with high porosity and GO membranes with
oxygen-containing groups, MoS2-based membranes still hold great
primes for the dye wastewater treatment based on the summary of this
section. Moreover, Chu et al., also demonstrated that the MoS2 mem­
branes with cations intercalation showed better water permeance than
previous reported GO, COF, MOF membranes under the similar rejection
condition [65].
4.2.2. Heavy metals removal
Heavy metals are one of the serious contaminants discharged from
industrial wastewater since they possess persistence, high toxicity in
water environment and are prone to be accumulated in body tissues
[118,119]. The novel 2D materials such as GO [120], transition metal
dichalcogenides [35], MOF and MXenes [121], were used to construct
2D-based membranes, which have been one of the promising membrane
techniques to treat heavy metals. Especially, MoS2 nanosheets with
intrinsic sulfur-rich characteristics and two types of atoms (i.e. Mo and
S) may show high selectivity and affinity for the heavy metal ions, and
Fig. 10. Performance and mechanism of MoS2 membranes in dyes rejection.[15] (a) the concentrations of organic dye (rhodamine-WT) in permeate, feed, and
retentate. (b) the effect of membrane thickness on dye rejections. (c) The proposed mechanism of dye rejection.
13
Chemical Engineering Journal 422 (2021) 130082
offer feasibility for tuning nanopores and/or nanochannel [36,122,123].
As for the nanoporous MoS2 membranes, the molecular dynamics
simulation was employed to investigate the removal of arsenic and
mercury ions from water [61,122]. The simulation results showed that
the rejection of two ions was related to the pore types and sizes. The fish-
bone nanostructure and an hourglass shape nanopore favored for the
high rejections [122]. As for other types of MoS2-based membranes, for
example, the composite membrane assembled by dithi-magnetospheres-
decorated MoS2 nanosheets and fragmentation chain transfer-
synthesized copolymer on the surface of a commercial RO membrane
was used to remove Pb2+ and As3+ from aqueous solutions, it was found
that Pb2+ and As3+ removal at 50 mg/L were respectively 95.3% and
96%, both of which were much higher compared to the pristine com­
mercial RO membrane. The narrow interlayer spacing offered by MoS2
nanosheets and dithizone-coated ferrite played an important role in the
enhanced removal of heavy metals. The positively charged NF mem­
branes with loading MoS2 nanosheets and polyethyleneimine were
examined to remove Cu2+, Zn2+, Mn2+ and Ni2+, the removal effi­
ciencies for these heavy metals was higher than 90% by the positively
charged MoS2 composite membrane on a ceramic hollow fiber [80].
Besides, the crystal structure and defects of MoS2 nanosheets could
greatly affect the membranes performance. It was reported that the
atomic-defect-rich 1 T-MoS2 nanosheets with sub-nanometer pores as
building blocks to prepare layer-stacked MoS2 membranes with high
permeability (181–345 LMH/bar) and separation performance for Pb2+
(84.5–99.6%) [36].
Recently, many efforts have been devoted to the recovery of heavy
metals from industrial wastewater [124,125]. MoS2-based membranes
as multifunctional membranes have been used to reject and recover
precious metals by one-step process. Wang et al., [35] found that the
layer-stacked membranes were able to achieve a high removal and
recover capacity of Ag+ (~4000 mg/g), a reduction–oxidation reaction
occurred between Ag+ ion and MoS2 nanosheets, the removal mecha­
nism is illustrated in Fig. 11a. In another study conducted by Zhao et al.,
[74], Pb2+, Hg2+, Cu2+, Au3+, Pd2+ and Ag+ as the typical contaminants
in industrial wastewater were filtrated by the MoS2-based membranes,
which was fabricated using MoS2 nanosheets and silk nanofibrils via
vacuum filtration. The removal capacities obtained under the optimal
Y. Liu et al.
condition were 153.5 mg/g, 249.4 mg/g, 22.2 mg/g, 759.1 mg/g, 425.1
mg/g and 246.2 mg/g, respectively. The removal of Pb2+, Hg2+, Cu2+
was attributed to the adsorption onto the hybrid membranes, while
adsorption & reduction could help to analyze the removal mechanism of
Au3+, Pd2+ and Ag+, the fabrication and removal mechanism is pre­
sented in Fig. 11b. The wastewater treatment and heavy metal recovery
could be simultaneously achieved, providing a promising technology for
zero discharge of wastewater in related industries (e.g. electroplating
industry).
4.2.3. Other contaminants removal
Apart from desalination and the removal of dyes and heavy metals,
more application in water treatment and purification have been devel­
oped even if MoS2-based membranes as a new membrane of membrane
family in few past decades. The organic micropollutants such as phar­
maceuticals and personal care products and endocrine-disrupting
chemicals have been widely detected in municipal and hospital waste­
water treatment plants and so forth [126,127]. It is nothing that the
design of conventional wastewater treatment technologies did not aim
at removing emerging organic micropollutants. Previous studies
demonstrated that membrane technique has been effectively imple­
mented to remove organic micropollutants especially for sustainable
water reclamation/reuse system [128]. MoS2-based membranes arise for
removing these pollutants. Ries et al., evaluated the retention of several
important micropollutants including caffeine, acetaminophen and ß-
oestradiol by the functionalized MoS2 membranes under the pressure of
2 bar at 0.05 M, 0.5 M and 11 μM, respectively [108]. The experimental
results showed that the rejection rates reached ~ 93%, ~94% and nearly
100% for caffeine (~0.38 nm of Stoke radius), acetaminophen (~0.39
nm of Stoke radius) and ß-oestradiol (~0.5 nm of Stoke radius), and the
water flux was higher than 3 LMH/bar. In another study, a novel
multifunctional MoS2-based membranes fabricated by a stack of MoS2
nanosheets with tunable interspacing using Fe(OH)3 nanoparticles [38].
The structure of ultra and conductive MoS2 nanosheets in the layer-
stacked membrane facilitated to anchor peroxymonosulfate and
trigger efficient electron transport, resulting in efficient generation of
reactive oxygen species (ROS). The degradation of Bisphenol reached
Fig. 11. Mechanism for removal and recovery of heavy metals by MoS2 membranes. (a) the removal and recovery of Ag+ ion. [35] (b) Strategy 1: Pb2+, Hg2+, and
Cu2+ ions; Strategy 2: Au3+, Pd2+, and Ag+ ions [74].
14
Chemical Engineering Journal 422 (2021) 130082
nearly 100%.
As well-known, the membrane process is a leading technology in
industrial wastewater treatment and reuse. The attempt of MoS2-based
membranes was made to apply for the treatment of landfill leachate
[109], which contained various of heavy metals, inorganic and organic
compounds [129]. Yadav et al., adopted GO, MoS2 and polyvinyl alcohol
to prepare a composite membrane on cellulose acetate membrane,
which was employed to treat landfill leachate from Whyte Gully located
in Wollongong, New South Wales, Australia [109]. The GO/MoS2-PVA
membrane exhibited high rejections for different ions with a moderate
permeability of 3.13 LMH at 5 bar, i.e. 90.23% for K, 94.51% for Ca,
98.29% for Mg, 96.54% for Al, 99.83% for Cr, 98.65% for Zn, 99.34%
for 86.54%, 91.71% for Pb, Th for 90.17%, respectively. Even if the
organic removal efficiency in landfill leachate was not reported in this
literature, it is speculated that the organic removal may be effective
according to the extremely high rejection rates of ions. Additionally, the
incorporated-MoS2 PES membranes was employed to treat the oil re­
finery wastewater[82]. The results demonstrated that the COD was
reduced from 240 mg/L to 40.8 mg/L and the turbidity was also
decreased from 12.2 NTU to 2.1 NTU after filtration of 160 min.
5. Antifouling properties
Membrane fouling, which is an unavoidable problem, occurs during
the filtration process when applying membranes for water treatment and
purification [1,16]. The extensive review papers have demonstrated that
fouling of membranes can be associated with feed water solution,
membrane materials and surface properties, operation conditions and so
forth [130-133]. Membrane materials play an essential role in allevi­
ating membrane fouling. The 2D-based materials have exhibited excel­
lent antifouling properties, the most popular nanomaterial is graphene
and its derivatives such as GO and rGO [9,132,134]. Obviously, MoS2
nanosheets, as a typical graphene-like nanomaterial, recently has drawn
increasing interest in improving antifouling performance, especially for
mitigating organic fouling and biofouling [39,81,117]. Before intro­
ducing MoS2 nanosheets for the fabrication of antifouling membranes, it
is necessary to understand antifouling properties of 2D materials. The
Y. Liu et al.
comparison has been made to estimate the antifouling properties of GO
and MoS2 by observing the bacteria and natural organic matter (NOM)
deposition using quartz crystal microbalance with dissipation moni­
toring (QCM-D) technique. Results indicated that the antifouling prop­
erties of MoS2 were stronger than those of GO, evidenced by lower
deposition of bacteria and NOM. This is due to the abundant functional
groups on GO, which could bind with the foulants [135]. The excellent
antibacterial activities also benefit the antibiofouling performance of
MoS2 membranes. Yang et al. firstly proved that MoS2 have good anti­
bacterial activities by generating ROS and inducing ROS-independent
chemical oxidative stress [136]. In addition, MoS2, as a representative
of two-dimensional (2D) nanomaterial, could induce physical damage
when contacting with bacteria due to the edges of 2D materials. MoS2
antibacterial surfaces have also been proven to be effective due to
contact-mode of action for antibacterial activities [137]. From the above
literature review on the properties of MoS2, we could know that MoS2
have great potential in mitigating membrane organic fouling and
biofouling. The current studies focus more on controlling organic
fouling and biofouling using MoS2 membrane, though inorganic fouling
is also one of the very important membrane fouling types.
5.1. Organic fouling control
The decline rate, total fouling, reversible fouling, irreversible fouling
and flux recovery ratio are commonly used to evaluate antifouling
abilities. Alam et al., [39] used sodium alginate and BSA as model
foulants to compare the antifouling performance of exciting 2D-based
membranes including GO, rGO and MoS2 membranes fabricated by
vacuum filtration on the PES substrate. The MoS2 membrane showed
better antifouling ability as compared to GO and rGO membranes in
terms of reversible fouling, i.e. 43% reversible fouling for MoS2 mem­
branes, 17% and 6% respectively for GO and rGO membranes. It was
because of that MoS2 nanosheets do not possess the conjugated struc­
tures to avoid cation-π and π-π interactions [18]. In contrast, functional
groups in GO and rGO structure were subjected to organic fouling.
Saraswathi et al., reported MoS2-incorporated UF membranes enhanced
the fouling resistance capability and had a very high BSA rejection rate
(92.3%) [40]. After that, there were several studies investigating the
antifouling behaviors on MoS2-based membranes, including layer-
stacked membrane, MoS2-incorporated membranes and membranes
surface modification with MoS2, the similar results were obtained
[81,83,112,117,138]. Interestingly, the TFC membrane with incorpo­
rated TA-MoS2 reported did not show obvious difference in antifouling
performance as compared to pristine TFC membrane [85]. This phe­
nomenon could be mainly explained by the balance between increased
hydrophilicity (beneficial for antifouling) and increased roughness
(unfavorable to antifouling) of membrane surface. Briefly, the hydro­
philicity, surface morphology, the negative charge and the structure
without conjugated groups play important roles in the control of organic
fouling.
5.2. Anti-biofouling properties
Biofouling is also one of the most tough problems to tackle for
membrane surfaces, thus to coat antimicrobial nanomaterials on the
membrane surfaces offers an opportunity to control membrane
biofouling. Two-dimensional (2D) nanomaterials could exhibit excellent
antimicrobial activities and are eco-friendly due to the contact mode of
antimicrobial action [134,139,140]. For example, Wang et al., recently
fabricated MoS2-incorporated membranes and investigated antibacterial
performance [81]. The MoS2/PES membrane showed good antibacterial
activities towards the Gram-negative bacteria E.coli and Gram-positive
bacteria B.subtilis with antibacterial efficiencies of 67.8% and 82.5%.
The antibacterial mechanism often involved two parts with 2D nano­
materials: one is the chemical oxidative stress, while the other is phys­
ical damage by the sharp edges on their surface. Once deposited on the
15
Chemical Engineering Journal 422 (2021) 130082
membrane surfaces, the chemical oxidative stress might not be able to
play a key role for the antibiofouling performance for the two-
dimensional nanomaterial membrane. However, the physical damage
by the edges of 2D nanomaterials will directly destroy the bacteria like a
knife. Thus, although not too many studies on using MoS2 to control
membrane biofouling were reported, it could be very interesting to
explore its potential since MoS2 have shown very good antibacterial
efficiencies [141-145].
6. Conclusion and outlook
In the past decades, MoS2-based membranes already have demon­
strated the excellent membrane performance, such as the enhanced
simultaneous permeability and selectivity, enable multifunctional
properties and antifouling ability. The recent advances of MoS2-based
membranes were reviewed, mainly including the design and fabrication
of three types membranes, i.e. nanoporous membranes, layer-stacked
membranes and MoS2 composite membranes, and their application for
desalination, industrial wastewater treatment, and antifouling proper­
ties: i) theoretical calculation and simulation studies have shown that
both high salt rejection and rapid water transport properties could be
achieved with nanoporous MoS2 membranes, but most studies focused
on both molecular dynamic simulation and experimental studies are still
lack. ii) As for the layer-stacked MoS2 membranes, the great advantages
are the high stability in aqueous solutions and the tunable interlayer
based on target separation species. The structural characteristics of
layer-stacked membranes such as crystal phase, interlayer spacing and
vacancy defect can offer a great promise for combining membrane
process with other water treatment technology such as advanced
oxidation process, photocatalytic and adsorption technologies. The
development of multifunctional membranes may be one potential di­
rection for research studies in the future. iii) The design and fabrication
of MoS2-incorporated and MoS2-surface modification membranes are
mostly based on these polymeric membranes. The combination of MoS2
nanosheets and commercial UF/NF/RO membranes has received much
attention for desalination, and the removal of some contaminants (e.g.
heavy metals, microorganic pollutants and oils) due to stability, facility,
efficiency and scalability of these membranes.
Overall, MoS2 nanosheets have the potential to significantly improve
membrane-based water treatment. MoS2-based membranes as a typical
2D-based membrane face the similar challenges in scaling-up production
and economic for practical applications. CVD method of monolayer
MoS2 may provide great potential for fabrication of defect-free and
large-scale. Besides, there exists a large amount of MoS2 in natural
molybdenite mineral, which facilitates to reduce the production cost.
Unlike commercial polymeric membranes and inorganic ceramic
membrane, common cleaning methods and agents (e.g. NaClO, HCl and
NaOH assist cleaning maintenance cleaning) may not be suitable for
MoS2-based membranes due to their relatively high chemical activity,
though related information are rarely involved in current research re­
ports. Therefore, novel cleaning strategies after unavoidable membrane
fouling need to be proposed. The membrane cleaning may take full
advantage of photochemical and electrochemical characteristics of
MoS2 nanomaterials. For example, light-induced ROS generation [146]
and electric-assisted free chlorine generation [135] could help to
enhance the degradation and release of membrane foulants. This might
provide a new direction for MoS2 membrane cleaning. Once MoS2
released into the aquatic environment, we should know the importance
of the potential environmental risk assessment that MoS2 might bring.
Overall, the research on MoS2-based membrane is underway. We hope
this review could contribute to give more comprehensive and in-depth
understanding for the design and fabrication of MoS2-based mem­
branes and their application in water treatment and purification.
Y. Liu et al.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by Shenzhen Municipal Science and
Technology Innovation Council of Shenzhen Government of China (No.
JCYJ20190809151215588); Guangdong Provincial Natural Science
Foundation of China (No. 2018A030313984); Tianjin Municipal Science
and Technology Bureau of China (No. 20JCYBJC00560); Research
Project of Tianjin Education Commission of China (No. 2019KJ103); the
Natural Science Foundation of Fujian Province of China (No.
2018J01526).
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