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Graphene-Based Membranes for Water and Wastewater Treatment:

A Review
Prangya Bhol,† Sudesh Yadav,† Ali Altaee,* Manav Saxena, Pramila Kumari Misra,
and Akshaya K. Samal*

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ABSTRACT: Increasing population and industrial growth,

combined with climate change, led to global water problems.
This review paper summarizes the next-generation hybrid
Downloaded via BUTLER UNIV on May 15, 2021 at 01:28:28 (UTC).

graphene-based membrane materials that are used for water

purification to meet global freshwater supplies. Graphene-based
membrane materials are believed to be the advanced materials for
the desalination process because of their atomic thickness and
tunable functionalities. The effect of membrane fabrication
techniques and operating conditions on the separation and
membrane fouling mechanisms are discussed in depth. The
present study discusses the development, advantages, and short-
comings of using hybrid graphene membranes compared to
traditional polymeric membranes. To extend the applications of
graphene membranes, more attention should be paid to the water permeability and membrane selectivity in long-term operation at
conditions similar to those in the field for performance analysis. While literature reviews have mainly concerned the ability of
graphene materials to adsorb water contaminants, there is very limited updated information related to its sieving properties.
Moreover, the literature lacks a comparative discussion of graphene-based membranes with other hybrid membrane materials. Thus,
a profound understanding of graphene-based membranes is much needed to unlock the potential for graphene materials. Also,
research interest in the preparation of the hybrid graphene membrane is expected to be explored in the future.
KEYWORDS: graphene-based membranes, conventional polymeric membranes, hybrid membrane materials,
nanoparticles and desalination

1. INTRODUCTION century.8,9 Compared to the conventional filtration methods,

Water is one of the valuable resources that improve the membrane filtration enables continuous operation with lower
sustainability of life on earth. The rapid growth of the world’s energy consumption at an affordable price.5,10 Several materials
population and the depletion of natural water resources have and developments have been adopted to design membranes in
worsened the problem of water scarcity.1 The global water recent years. Since in the early 1960s, organic polymers are
demand has been estimated to continue at a similar growth dominating the membrane industry. However, most of the
membrane processes for water and wastewater treatment rely
rate until 2040, projecting a 20−30% increase from existing
on a polyamide thin-film composite membrane that was
water consumption (Figure 1).2,3 There are various physical
developed 4 decades ago (Figure 2).11
and chemical technologies for water and wastewater treatment
Unfortunately, low chlorine tolerance, fouling, limited water
such as gravity separation, membrane filtration technologies,
flux, and separation efficiency are some of the major drawbacks
air flotation, absorption materials, chemical vapor deposition
of traditional polymeric membranes.6,12 The drawbacks of
(CVD), coating mesh, carbon-based materials, hydrophobic
conventional polymeric membranes can be eliminated by the
aerogels, a sol−gel process, and sponges.4,5 These technologies
can remove a large proportion of dissolved ions.6 Still, they
have some inherent limitations such as low separation or Received: December 24, 2020
rejection rate, fouling, high energy consumption, reusability, Accepted: March 10, 2021
and recyclability of the filtration media.7 Further, conventional Published: March 23, 2021
filtration methods, including distillation, adsorption, chlorina-
tion, coagulation, and flocculation, are incapable of producing
high-quality water to meet the global demands of the 21st

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Figure 1. Global water demand by various sectors from 2014 to 2040 (projected). Modified by authors and reproduced with permission from ref 3.
Copyright 2019 International Energy Agency.

Figure 2. Trends and developments in membrane materials from 1960 to the present.

hybrid nanoporous membrane because it has continuous properties. Further, because of its unique lattice structure,
channels that allow a high volume of water to pass at low graphene has become a fascinating functional membrane
operational pressure.9 With the integration of nanoparticles, material for water purification.16,17 In addition, a broad range
the permeability and selectivity trade-off for polymeric of graphene derivatives have been studied to improve further
membranes could be eliminated; for instance, an increase in the graphene material capability. Graphene oxide (GO) has
the permeability rate for gas separation was observed for silica become one of the main derivatives of graphene that retains a
nanoparticle-incorporated polysulfone (PSf) membranes.13 substantial portion of the graphene characteristics.18 Because
The addition of nanoparticles within the polymer matrix of the presence of polar oxygen-containing functional groups,
could improve the stability of the polymer membrane’s GO is water-dispersible. During the preparation, the degree of
permselectivity at high temperature.14 However, the fine oxidation in GO can be customized, which is crucial for a
dispersion of nanoparticles in the vicinity of polymers is the successive alteration of the graphene derivatives.19
main drawback of these hybrid polymer membranes.15 Specifically, functionalization implies the covalent bonding
Therefore, a breakthrough in membrane development is of functional groups on the surface of the graphene sheet,
much needed for resolving the water challenges of the 21st whereas doping is the introduction of heteroatoms like
century.12 nitrogen (N), sulfur (S), and fluorine (F) into the carbon
Two-dimensional (2D) graphene materials have excellent lattice of graphene.20,21 Both functionalization and doping will
mechanical strength, thermal conductivity, and electrical tailor the properties of graphene for a wide variety of high-
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performance applications, including membrane technology.22 Graphene-based frameworks with polar functional groups have
Furthermore, GO derivatives show exceptional membrane been considered to be a key property of nanotechnology to
properties such as antifouling, high chlorine tolerance, and obtain an ideal membrane.32,33 Further, the incorporation of
antimicrobial activity, thus improving the membrane lifetime.4 these nanomaterials provides frictionless capillary channels,
Fouling-resistant membranes with tunable surface function- which further enhances the permeability speed within the
alities have an enormous potential to eliminate the pretreat- membranes.
ment process, which decreases the energy consumption of 2.1.1. Fabrication and Functionalization of GO-Based
desalination plants to a greater extent.23 Currently, graphene Membranes. GO membranes tend to self-assemble by simple
membranes have shown huge potential for brackish water filtration with GO solutions, layer-by-layer (LBL), drop-
treatment using a nanofiltration (NF) membrane.24,25 casting, and dip coating.34 The packing structure of GO
Molecular simulations and theoretical studies show the laminates can be tuned depending on the assembly using
applicability of graphene membranes for reverse osmosis different methods. The filtration method is considered to be
(RO) desalination.11 one of the simple and common approaches where a hydraulic
This review summarizes the most recent developments of pressure or vacuum is applied on GO nanosheets to narrow the
fabrication methods for preparing graphene-based membranes interlayer spacing. GO paper by filtering out the GO solution
of the existing literature. Initially, the study briefly introduced through a microfiltration membrane was engineered,35 and X-
GO and carbon nanotube (CNT) membrane materials. Then, ray diffraction patterns showing 0.83 nm of layer-to-layer d
factors governing the transport mechanism in graphene spacing of the GO paper were confirmed. The interlayer
materials are reviewed. The major objective of this review is spacing (d spacing) increases with an increase in the degree of
to discuss the hybrid graphene membrane performance oxidation and reaches around 1 nm.36 The pure graphene
compared to that of other advanced nanomaterials and poses an interlayer spacing of 0.34 nm, which is sufficient to
polymeric nanocomposites with exemplified illustrations. allow a single layer of water in between.37 Further, the d
Finally, future research directions and bottleneck challenges spacing may change in GO, upon hydration, or provided an
of graphene membranes are discussed in detail. environment with high humidity.38 Water-transport channels
are supplied by d spacing with a size-exclusion property for
2. GRAPHENE-BASED NANOMATERIALS small size molecules. A chemically converted method is
The 2D graphene and its derivatives are building blocks for followed to fabricate graphene-based membranes for studying
advanced membranes. The graphene consists of sp2-hybridized the corrugation of GO nanosheets and conclude that GO
carbon (C) atoms positioned in a hexagonal honeycomb nanosheets possibly can be used to fabricate NF membranes.39
lattice.16 Recently, graphene-based nanomaterials like zero- The rejection rate of 67% was achieved for direct yellow dye.
dimensional carbon quantum dots, one-dimensional (1D) Hence, it is possible to prepare the NF membrane by simply
CNTs, 2D GO, and reduced graphene oxide (rGO) have filtering out a GO solution from a microporous membrane.
drawn incredible consideration from researchers around the GO membranes were studied to determine the permeability of
globe.23−27 In addition, when these are assembled into the membrane and found to be unhindered during the
multilayered structures, the separation efficiency is enhanced. permeation of water, while they highly blocked hydrogen,
2.1. GO-Based Membranes. The presence of C sp2 nitrogen, argon, and helium.37 The cause for fast water
(aromatic) and sp3 (aliphatic) with oxygen-containing func- penetration into the multilayered GO membranes was due to
tional groups in the GO structure allows chemical reaction and the channels opposing the slower solution-diffusion water-
surface modification to form distinct assembly morphologies transport mechanism in membranes. Numerous methods were
for specific application of the separation performance.28 The developed for the fabrication of GO separation membranes,
existence of polar functional groups allows GO better out of which the most common methods, such as casting/
hydrophilicity and stable dispersion in an aqueous medium.17 coating, LBL, and vacuum/pressure-assisted self-assembly,
The possible production of large-scale GO and its inexpensive- have been discussed in the following sections.
ness allow GO to be effectively studied. Controlling the degree 2.1.1.1. Casting/Coating-Based Method. The direct and
of oxidation, size, and functional groups in the controlled simple approach in the deposition process makes the cast/
synthesis of GO helps one to study and understand the coating method the most common method for the fabrication
separation mechanism of the lamella arrangement, resulting in of GO membranes. The cast/coating process has a broad
a high separation efficiency.29 variety of options on a substrate, particularly in the design of
Recent studies depicted that graphene has the potential for freestanding GO membranes. GO laminates over the copper
application for the fabrication of a highly selective and foils using the coating process, and carving them out produces
permeable separation membrane with a better performance a freestanding GO membrane.37 GO membranes were
for water purification compared to an inorganic filtration or a fabricated through drop-casting over a portion of smooth
polymer-based membrane. Nevertheless, major graphene- paper. Then the freestanding GO membrane was stripped from
based membranes showing high permeation flux were prepared the supported paper. Additionally, on the basis of charged
by decreasing their thicknesses to the extent of <50 nm. hollow membranes, the deep coating can be employed for the
Astonishingly, to enhance the permeability of membranes, fabrication of selective thin barriers.40 A comparative study of
graphene-based materials are modified using nanomaterials two coating methods for testing the relative effect of
and have become a promising alternative. The nanomaterials electrostatic repulsion and immersion capillary force over the
can range from inorganic nanoparticles to organic mole- stacking GO configuration was carried out.41 During the
cules.30,31 The above-mentioned low-dimensional graphene process, the base membrane was kept in contact with the
nanomaterials with tunable functionalities and enhanced interface of air−liquid in the GO solution, where GO
surface properties facilitate the membrane modification as a membranes were synthesized via direct spin coating. Highly
trade-off between the permeability and selectivity properties. dense GO deposition occurred in the spin-coating process
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because attractive capillary forces surmount the repulsive morphology with fine mechanical strength by depositing GO
interactions. and 1,3,5-benzenetricarbonyl trichloride over a polydopamine-
2.1.1.2. LBL Self-Assembly Method. The LBL self-assembly coated PSf support.16
method can generate a thin film charged at the molecular level 2.1.1.3. Vacuum/Pressure-Assisted Method. GO material
by accumulating polyelectrolytes of opposite charge.42 LBL possesses hydrophilic and negatively charged oxygen functional
membranes consist of polycations and polyanions that deposit groups like epoxy, hydroxyl, and carboxyl groups that are well
over the substrate via electrostatic interaction. For a LBL self- dispersed in the aqueous medium without aggregation, because
assembly technique, GO can be an appropriate choice because of which a vacuum/pressure-assisted method is suitable for the
it poses a laminar configuration as well as a functional group design of GO membranes with multilayers. Both vacuum and
with charged oxygen. In the process, first the substrate is pressure-assisted methods are filtration techniques wherein
modified to become a charged surface and then the LBL there is simultaneous deposition of GO nanosheets in a parallel
process starts. Zhang et al. cross-linked the substrate layer with manner on the base membranes, counting the ultrafiltration
hyperbranched polyethylenimine (HPEI) along with repeated and microfiltration membranes. Upon alteration of the volume
dipping and soaking of the membrane in a GO and or concentration of the GO precursor solution, the thicknesses
ethylenediamine (EDA) solution for further deposition cycles of GO membranes can be tuned in the vacuum/pressure-
of GO and EDA (Figure 3a).43 Positively charged HPEI alters assisted method. A comparative study of GO microstructures
was designed using pressure-, vacuum-, and evaporation-
assisted self-assembly methods, and it was concluded that GO
membranes formed from a pressure-assisted fabrication
method exhibited aa highly controlled laminar morphology
with the lowest surface roughness.34 For instance, Cheng and
co-workers prepared GO/polyacrylamide membranes for
organic dye separation using a vacuum filtration method.
The GO/polyacrylamide membrane shows 0.68 nm interlayer
spacing, with 95.43% rejection for a rhodamine B (RhB) dye
solution, 45 whereas GO membranes formed from an
evaporation-assisted fabrication method displayed maximum
roughness and water contact angle compared to the other two
methods.
Transmission electron microscopy (TEM) shows that the
orientation of the pressure-assisted GO membrane is highly
organized (Figure 4a). In contrast, the evaporation-assisted
membrane possessed ring morphology with random orienta-
tion (Figure 4c). The formation of a ring morphology in the
evaporation-assisted membrane indicates the hydrophobic
nature of the membrane. Controlling the deposition rate can
improvise the channel structure in the pressure-assisted GO
membranes. When the deposition rate is reduced, it results in
more oxidized patches, consequently forming spots free of the
functionalized group. The highly ordered GO membranes
displayed simultaneously high rejection and flux (Figure 4d).46
Some of the recent studies and performances of GO-based
Figure 3. Schematic illustrations of different methods for the design membranes are tabulated in Table 1.
of a LBL GO membrane. (a) Alternative dipping into two solutions From the above, it is observed that versatile techniques and
for the production of a LBL GO membrane. Reproduced with strategies exist to design GO-based membranes having certain
permission from ref 43. Copyright 2016 Elsevier. (b) Design of a LBL advantages and disadvantages in real-time applications,
GO membrane of sandwich structure by using polyelectrolyte as the depending on the mechanical strength, porosity, nanochannel
cross-linker between GO and CNT. Reproduced with permission type, and chemical inertness. GO membranes prepared by
from ref 44. Copyright 2018 Elsevier. pressure-, evaporation-, and vacuum-assisted methods may
result in roughness on the nanosheets. The evaporation-
the surface property. A similar LBL self-assembly technique is induced self-assembly method utilizes the π−π-stacking
also useful for assembling two nanomaterials to form a interaction among of GO primitives to form thin and large
multilayered configuration. GO membranes in a sandwich graphene-based films. Highly ordered GO membranes can be
structure were produced,44 and the d spacing in the GO LBL prepared following the evaporation-induced self-assembly
membrane was successfully altered. In the process, alternative method. The pros and cons of various fabrication techniques
layers of GO and oxidized CNT were stacked on one another for graphene-based membranes are shown in Figure 5. Further,
to form a sandwich morphology, which was afterward cross- capillary-force-assisted self-assembly helps one to form a highly
linked with the help of a polyelectrolyte (Figure 3b). The packed, well-ordered dense morphology and enhances the
presence of oxidized CNTs highly accelerates the permeability conductivity compared to vacuum-filtration-prepared mem-
and roughness on the membrane surface. In addition to branes. Thus, a higher rejection rate is expected for various
electrostatic attraction, the cross-linking and electric field have contaminants compared to the less ordered vacuum filtration
also been utilized to fabricate LBL GO membranes. Further, membranes. Stacked GO membranes with lamellar morphol-
Hu and Mi produced a GO membrane of cross-linked ogy possess extreme advantages like ease of scalability, high
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Figure 4. (a−c) TEM morphologies of GO membranes synthesized via (a) pressure-, (b) vacuum-, and (c) evaporation-assisted methods.
Reproduced with permission from ref 34. Copyright 2015 Elsevier. (d) Interlayer nanostructures of GO membranes fabricated by slow and fast
deposition rates. Reproduced with permission from ref 46. Copyright 2017 American Chemical Society.

Table 1. Summary of the Properties and Performances for GO Membranesa

GO properties Substrate Membrane performance
Interlayer space Water permeance
O/C (nm) Type Pore size Thickness (LMH/bar) Rejection Ref
NA NA PVDF 50 nm 44.1 mg m−2 7.64 98.3% Na2SO4 47
NA 0.86−1.12 nylon 0.22 μm NA 51−60 99% MB, 99.82% CR 48
∼2.39 0.76 PES NA 1.36 μm 13.4 ∼80% MB, ∼80% RhB 49
NA 0.65−0.75 PES 0.03−0.2 μm NA ∼30 89.8% MR, 99.4% MB, 96.8% BBG, 72.6% EB, 50
63.9% RhB
NA 0.766 MCE 0.2 μm 478 mg m−2, 10.7 ∼35% NaCl 51
86.5 nm
NA 0.64 CA 0.2 μm NA 0.592−1.416 ∼89% NaCl 25
∼0.5 0.9 MCE 0.2 μm 478 mg m−2, 11.0 ∼30% NaCl 52
330 nm
0.4 NA PC NA 69.41 ± 3.85 nm ∼5 ∼70% Na2SO4 7
1.61 0.82−0.84 AAO NA 4.7 nm, 23.6 nm 7−20 ∼60% MgSO4, ∼30% NaCl 46
NA 0.899 PC 200 nm ∼20 nm 6.3 20% NaCl 53
0.4 0.796 PES 30 nm ∼20 nm 7.37 57.73% Na2SO4 54
a
NA = not available; CA = cellulose acetate; AAO = anodic aluminum oxide; PVDF = poly(vinylidene fluoride); PES = poly(ether sulfone); MCE
= mixed cellulose esters; PC = polycarbonate; Na2SO4 = sodium sulfate; MgSO4 = magnesium sulfate; NaCl = sodium chloride; MB = methylene
blue; CR = Congo red; RhB = rhodamine B; MR = methyl red; BBG = brilliant blue G; EB = Evans blue.

separation efficiency, and water permeability and can be large-size organic molecules were blocked by the nanochannels
intensely applied for NF and RO. However, depending on the inside the GO membranes.8 Water molecules can pass through
preparation technique, the desired GO membranes can be GO by taking a tortuous pathway (dotted line) inside the
developed for the specific application for liquid separation. vacant space of oxidized regions among GO sheets (with a thin
2.1.2. Transport Mechanism for GO-Based Membranes. d spacing). The water molecules move across all of the
To understand the mechanism of GO separation, several oxidized regions (from top view), reach the next interlayer
studies were carried out on GO membranes. In GO-based NF space (from side view), and move around the GO sheets (with
membranes (Figure 6II), because of the size barring effect, longer dimensions L; Figure 6I).37
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Figure 5. Schematic representation of the pros and cons of various fabrication techniques for the preparation of graphene-based membranes.

Figure 6. (I) Transport channels in GO membranes. (II) GO membrane separation mechanism by (a) size exclusion, (b) Donnan exclusion, and
(c) adsorption. Reproduced with permission from ref 8. Copyright 2017 Elsevier.

Particular size exclusions to ionic and bigger molecules can and charged ions can also be restricted by following the
be obtained by tuning the spacing of the GO nanochannels,55 Donnan exclusion of GO membranes.56,57 GO is negatively
because of which GO membranes are mostly used to design charged in the broad pH range because the carboxyl groups
membranes with fine interlayer spacing with the insertion of undergo deprotonation from the edges of the GO nanosheets.
cross-linkers or nanofillers of a particular size for water This allows GO membranes to be efficiently separated with
purification, pharmaceutical separation, and wastewater reuse. high rejection for negatively charged organic molecules as well
The GO membranes are reduced with the help of reducing as divalent ions.27 The negatively charged features of GO
agents, providing small-sized nanochannels and better membranes were altered by incorporating amine-abundant
membrane hydrophobicity. The passage of smaller molecules molecules such as polyamidoamine dendrimer and HPEI7 to
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Figure 7. Water transport and rejection mechanism of current state-of-the-art functional CNT membranes: (a) VA-CNT; (b) MM-CNT; (c) HA-
CNT. Reproduced with permission from ref 66. Copyright 2019 Elsevier.

produce positively charged GO framework membranes for including membrane-based separations.61,62 Because of the
heavy-metal rejection, which displays an efficiency of 95%. presence of rolled graphene and lamella columns, water
Various smaller hydrate ions adsorb strongly on different molecules can travel at a higher magnitude compared to other
regions of GO sheets through various interactions, leading to materials with similar pore sizes. The molecularly smooth
excellent selectivity with GO membranes. This is possible hydrophobic graphene surface provides frictionless capillaries
because the transition-metal cations could coordinately for water permeability.63
interact with oxygen-containing functional groups and be 2.2.1. Fabrication of CNT-Based Membranes. On the basis
blocked by GO membranes.40 Likewise the interaction of alkali of the fabrication technique, CNTs are classified into three
and alkaline-earth cations with the sp2 cluster of GO via classes such as mixed matrix (MM-CNT), vertically aligned
cation−π interactions can decrease the permeability of alkali (VA-CNT), and self-standing CNT bucky paper (CNT-BP)
and alkaline-earth cations across GO membranes.58 membranes (Figure 7). MM-CNT and CNT-BP membranes
2.2. CNT-Based Membranes. Graphene layers rolled up hold a random distribution of CNTs on a huge porous
to form thin hollow cylinders with open or capped ends are structure, whereas in VA-CNT membranes, the CNTs are
known as CNTs. CNTs exhibit outstanding properties like perpendicularly arranged in a line over a substrate for the
high aspect ratio, high mechanical strength, large specific passage of fluid through the interior of the CNT or among the
surface area, low tortuosity, and smooth morphology. The CNT bundles.59 CNT-BP membranes are produced into a
diameter of CNTs can be tuned, offering controllable porosity paperlike morphology of a CNT mat using the self-assembly
in the structure that can be employed for various separation method. The stability of the CNT mat is due to the presence
activities.59 CNTs exhibit excellent thermal and electrical of van der Waals forces as well as π−π interactions among the
conductivity and are considered to be some of the strongest attached nanotubes, which offers a highly porous 3D network
fibers. Membranes based on CNTs can be designed into and a large specific area.64 Further, the CNT membranes can
variant structures, which could offer unlimited advantages in be aligned horizontally over a substrate during the fabrication
the membrane performance. For instance, cylinders formed by technique, forming horizontally aligned CNT (HA-CNT)
multiple layers are referred to as multiwalled CNTs membranes.65,66
(MWCNTs), while a few layers (1−10) of graphene form 2.2.1.1. VA-CNT Membrane. CNT with hollow morphology
single-walled CNTs (SWCNTs). SWCNTs possess diameters can be utilized to remove various emerging pollutants from
of up to 1−3 nm and inner diameters of 0.4−2.4 nm. wastewater.67 Hinds and co-workers developed a multiwalled
MWCNTs possess outer diameters varying from ∼2 nm VA-CNT membrane consisting of a pore diameter of 6 nm
(double-walled nanotubes) to ∼100 nm consisting of tens of with CNT fillers incorporated into the polystyrene film.68 In
walls.19 MWCNTs are coaxially arranged, and the d spacing general, manufacturing VA-CNT membranes requires the
between graphene layers is found to be similar to that of organization of CNTs perpendicular to the organic or
graphene at about ∼3.4 Å.60 inorganic support layer, as shown in Figure 7a.27 The CVD
On the basis of the orientation of graphene layers, several technique facilitates the vertically aligned growth of the CNT
configurations are possible for CNTs like a chiral, armchair, forest over the support layer, which is useful for designing fine
and zigzag. Inner hollow cavities with nanoscale diameters membrane structures. Afterward, polystyrene, parylene, or
make CNTs an ideal candidate for several applications epoxies are filled in the space between the nanotubes to restrict
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Figure 8. Cross-sectional SEM morphology of (a) GO, (b) GO/CNT, and (c) GO/AC membranes and TEM images of (d) GO, (e) GO/CNT,
and (f) GO/AC membranes. Reproduced with permission from ref 85. Copyright 2017 Nature Research.

water leakage.69 Afterward, the extra fillers are removed from functional CNTs with good dispersion properties over the
the surface via an etching method to open the CNT tips, membrane substrate.77
forming fine porous CNT membranes. The membranes A new sulfonated MWCNT (S-MWCNT) membrane was
possess a high sieving capacity for the various pollutants developed by Zheng and co-workers by the IP method.78 To
present in water. However, large-scale production of VA-CNT prepare a S-MWCNT, a hydroxylated MWCNT was used to
is difficult because it requires the alignment of CNTs in larger disperse in a solvent. The addition of 0.01% S-MWCNTs to
surface area, restricting its real-time application in large-scale the membrane exhibited a maximum salt rejection of 96.8%
water treatment processes. This can be overcome by following with an outstanding water permeability of 13.2 L m−2 h−1
the electrocasting technique for fine alignment of MWCNTs bar−1. Free amine, carboxyl, and other negatively charged
over the substrate.70 Wu and co-workers developed this functional groups on the surface of the polyamide membrane
approach for aligning MWCNTs on a polystyrene membrane act as binding sites for the CNT when loaded on polyamide
using an alternating electric field of 2000 V cm−1.70 The membranes.79
MWCNTs/PS nanocomposite membranes were prepared 2.2.1.3. HA-CNT Membranes. HA-CNT membranes require
using the newly developed electrocasting method. The analysis horizontal placement of CNTs on the support layer, which
was carried out in different frequency ranges (from 1 to 100 often results in the random orientation of CNT materials on
Hz), and the highest MWCNT dispersion and good VA-CNT the porous active layer (Figure 7c). Two steps are followed for
membrane permeability were achieved. Further, Lee and co- the fabrication of HA-CNT membranes in which the
functionalization of CNTs and the manufacture of HA-CNT
workers developed a new VA-CNT membrane in which
structures via vacuum filtration of the CNT dispersion are
interstices between CNT fillers are used to eliminate the
used. Step 1 involves the employment of functional CNTs to
contaminants instead of the void channels of CNTs and
enhance the homogeneous dispersion of CNTs in the solvent
termed as outer-wall CNT membranes.71 via ultrasonication. In step 2, dispersed functional CNTs are
2.2.1.2. MM-CNT Membranes. Randomly aligned CNTs fabricated over a substrate membrane, followed by drying out
into the polymeric matrix are known as MM-CNT membranes the solvent in the oven.69 The random orientation of CNTs
in which a CNT serves as the inorganic filler.72 Such a over HA-CNT membranes generates a good porous
heterogeneous morphology provides excellent permeability morphology and high specific surface area,77 resulting in a
and selectivity because of the combined characteristics of CNT greater adsorption capacity for natural organic pollutant80 and
and polymeric membranes, which result in high-permeability strong antimicrobial activity.81
and selective membranes.73 The greater antifouling propensity 2.2.2. Functionalization of CNT-Based Membranes. CNT
and filtration capacity of MM-CNT membranes have led functionalization is indeed a precondition for CNT membrane-
researchers to focus more on its water treatment process.74 based desalination and wastewater treatment. Pristine CNTs
The fabrication of MM-CNT membranes involves an are hydrophobic and tend to accumulate on the surface, which
interfacial polymerization (IP) or phase inversion process results in the permeance−selectivity trade-off. The poor
(Figure 7b) in which the functional CNTs are added straight stabilization and dispersion of CNTs in solvent media limit
to the polymeric membranes.75,76 These membranes are their application in water purification. However, these are very
outstanding in ultrafiltration or forward osmosis or in the much compatible with hydrophilic graphene-based materials to
RO process.69 However, this method involves a certain form a hybrid membrane. When employed for water
drawback that is the dispersion of CNTs over the support purification, it has shown greater adsorption capacities and
membrane matrix, which is being dominated by employing high filtration efficiency for the elimination of pollutants from
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Figure 9. (a) UV−vis absorption spectra of the GO-, GO/CNT-, and GO/AC-filtered initial TCH and residue solutions: (b) pure GO, (c) GO/
CNT, and (d) GO/AC membranes and (e) the CNT/AC hybrid. (f) Transport mechanism route for the TCH solution through contact with the
GO/AC membrane. Reproduced with permission from ref 85. Copyright 2017 Nature Research.

water. In general, metal catalysts are used for CNT and CNTs, microchannels in the hybrid membrane formed,
functionalization.82 Further, capping agents are used to accelerating the water flow across the membranes. Therefore,
facilitate the selective functionalization of capped CNTs. The the hybridization approach leads to improvement in the
surface charge and properties can be tuned with the help of separation efficiency and permeability.
functionalization.83 Functionalized CNT membranes show In another study, CNTs were made dispersible with the help
better activity such as permeability, selectivity, and fouling of a F127 surfactant.22 The finely dispersed 1D CNTs were
resistance.84 incorporated into 2D graphene sheets to shape a homogeneous
Hybrid membranes comprised of 2D GO sheets, 1D CNTs, network. The dispersed CNTs remarkably affected the rGO/
and activated carbon (AC) for the removal of tetracycline CNT hybrid NF membrane performance. When the hybrid
hydrochloride (TCH) antibiotics from water were studied.85 A membrane was subjected to drinking water, it showed excellent
freestanding and flexible membrane was produced from GO, retention efficiencies (more than 99%) and permeabilities of
GO/CNT, and GO/AC by following a facile vacuum filtration 20−30 L m−2 h−1 bar−1 of dyes, bovine serum albumin (BSA),
method. The GO membrane possessed a dense structure with nanoparticles, humic acid, and sugars. The NF displayed nice
uniform dispersity of CNTs within GO flakes, which might be retention and high flux for Au nanoparticles, BSA, and phoxim
due to the van der Waals force of interaction between them with retention of 99.2%, 99.5%, and 99.8%, respectively.
because of which GO/CNT exhibited maximum porosity Hence, the rGO/CNTs are effective hybrid NF membranes for
compared to pure GO (Figure 8). drinking water purification. Further, TiO2 is one of the
The absorption capacity of the membranes was studied promising semiconducting materials that promotes advanced
using UV−vis spectra of a TCH solution (20 mL, 1 mg mL−1) oxidation processes in the water treatment process. TiO2 are
and residue solutions of TCH (Figure 9a) after filtration with inexpensive, catalyst inert in nature, and photostable.86 Titania
GO, GO/CNT, CNT/AC, and GO/AC membranes. The possesses a band gap of 3.2 eV in its anatase phase and can
TCH solution displayed a strong absorption band in the UV produce an electron/hole pair when light of wavelength below
region, while the GO-membrane-filtered TCH residue solution 380 nm is absorbed.87,88 Polymer membranes impregnated
displayed a huge fall in the absorption peak compared to the with TiO2 are more hydrophilic compared to the unaltered
TCH solution. Whereas the GO/CNT and GO/AC TCH polymer membrane and show improved antifouling character-
residue solution showed an even larger fall in the absorption istics. For example, PAA-grafted PVDF with TiO2 has a lower
intensity compared to TCH and GO-filtered TCH residues, contact angle than that of the pure PVDF membrane.89
which depict the higher adsorption ability of GO/CNTs However, the degree of antifouling was not proportional to the
compared to GO/AC and GO for TCH. The enhancement in degree of hydrophilicity of the membrane.
the adsorption ability arises because of the porous structure When the NF membrane coated with 0.01 wt % TiO2
that emerged within GO when CNTs and AC are incorporated showed a greater flux compared to a 0.03 wt % coating of
in the interstitial sites of GO nanoflakes. The addition of TiO2, even though the 0.03 wt % TiO2 coating enhanced the
CNTs and AC develops microchannels in the hybrids, hydrophilicity. Hybrid PSf/nano-TiO2/MWCNT ultrafiltra-
resulting in an acceleration in the water flow through the tion membranes incorporating variable nanoparticle ratios
membrane. Hence, better permeability and selectivity were [total filler content at 1% (w/w)] were produced and
achieved by hybridizing with CNTs. Parts b−f of Figure 9 fabricated using the phase inversion method.90 The study
illustrate the mechanism for acceleration of the GO/NT and showed the effects of the TiO2/MWCNT nanoparticles ratio
GO/AC membranes. A better performance of GO/CNT and on the pore size of the membrane, membrane morphology,
GO/AC was obtained compared to the pristine GO membrane rejection of humic acid, and permeation fouling. The addition
because GO possesses strong π−π stacking, as shown in Figure of TiO2 and MWCNT generates fingerlike interconnected
9b. When pure GO was incorporated with CNTs and AC in pores, forming a greater number of pores on the surface of the
the interstitial sites, a porous structure rose in the vicinity of membrane. The study revealed a higher TiO2 composition and
hybrid membranes, as shown in Figure 9c,d. However, CNT/ displayed a lower flux decline in the presence of humic acid,
AC possesses poor mechanical strength and develops cracks while a higher amount of MWCNT in the membrane also
and gaps within a few minutes after formation. Figure 9f shows enhanced the pore size with greater pure water flux. When the
the water permeation route for a TCH solution. Because there two nanostructures of TiO2 and MWCNT are combined [e.g.,
is an increase in the porous structure with the insertion of AC 0.5% TiO2 and 0.5% MWCNT (w/w)], moderate permeation
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and rejection rates for the 2 ppm humic acid feed solution are Filice and co-workers prepared a hybrid Nafion composite
displayed. When the two nanomaterials are present in membrane and studied its application in the degradation of
equivalent percentages (e.g., the 0.5%/0.5% mixture), they water pollutants.86 The membrane properties were tuned using
offer flexibility and improvise the membrane characteristics.90 some suitable fillers such as organo-modified GO (GOSULF),
2.2.3. Transport Mechanism for CNT-Based Membranes. GO, and TiO2 nanoparticles associated with the advantage of
The nonpolar inner shell of the hollow cylinder consisting of membrane application and photocatalysis. The photocatalytic
carbon molecules provides a spontaneous and unbridled and adsorption property of the membrane was studied using an
passage of water molecules with low adsorption. VA-CNT azo dye, methyl orange (MO). MO dipped in the membranes
membranes are predominantly studied for membrane showed a decrease in concentration in both dark and
fabrication. The pore radius plays a key role in the irradiation conditions, but a stronger effect was observed in
permeance−selectivity trade-off consisting of aligned the case of irradiation. The Nafion/TiO2 and Nafion/GOSULF
CNTs.91 Previous studies based on molecular dynamics performances were greater compared to the photocatalytic
simulations have suggested a direct correlation between the performance of fillers dispersed directly in the MO solution.
low surface friction and permeability of CNT membranes.92,93 Under irradiation, Nafion/TiO2 degraded MO to form
Longhurst and Quirke92 observed an upshift in the radial byproducts. Nafion/GOSULF was very efficient in the removal
breathing mode frequency when the CNT surface interacts of dye, and even after 3 h under a UVA/blue lamp, the
with water molecules. Hummer et al.94 studied the pulse-like concentration of residual MO was lower than 30% from its
transmission of water through the CNT channels because of starting value without forming any toxic byproducts in the
the formation of strong intramolecular hydrogen bonding solution (Figure 11).
between water molecules. Besides, the interaction between the 2.3.2. GO/Polymer Hybrid Membrane. GO consists of
water molecules and inner CNT shell has a huge influence on lamellar morphology with thicknesses of about 1−30 μm with
the pore hydration of rigid hydrophobic hollow cylinders.94 polar functional groups of carboxyl- and hydroxyl-containing
The observations suggest new research directions to unlock the negatively charged oxygen.95 The presence of polar functional
molecular sieve mechanism of CNT membranes. groups allows it to disperse stably in water without any
2.3. Hybrid Graphene-Based Membranes. 2.3.1. GO/ addition of a stabilizer.96 The interlayer spacing of GO
TiO2 Hybrid Membranes. TiO2 exhibits excellent photo- membranes can be easily tuned with the insertion of organic
catalytic oxidation and antifouling characteristics when it is polymers such as water-soluble polyacrylamide. Polyacryla-
subjected to organic wastewater treatment and exhibits mide, being a polycation, can be used as a binder and to
remarkable performance. For example, Gao and co-workers synthesize a hybrid membrane with negatively charged GO.
synthesized the GO/TiO2 microsphere hierarchical membrane Cheng and co-workers prepared the GO/polyacrylamide
(Figure 10) by accumulating the GO/TiO2 microsphere membrane by following the vacuum filtration method.45 A
stacked multilayer morphology consisting of numerous
channels in the cross-sectional layers of the GO membrane
was obtained. Further, the interlayer spacing was tuned by
incorporating the organic polymer PAM. From the perform-
ance studies, it was observed that the water flux was inversely
related to the thicknesses of the membranes and the retention
was directly related to the thickness of membrane. A 95.43% of
rejection rate was obtained by the GO/polyacrylamide
membrane, whereas the pristine GO membrane showed
85.03% rejection for the RhB dye. Because RhB is an anionic
dye and the GO membrane is negatively charged, it is difficult
to adsorb an anionic dye by the GO membrane, but when it is
Figure 10. Field-emission SEM image of the GO/TiO2 membrane hybridized with polyacrylamide, the surface negative charge
surface after filtration: (a) membrane surface without UV irradiation reduces as a result of a decrease in the inhibition effect for the
(inset: digital photograph of the GO/TiO2 membrane); (b) adsorbing anionic dye.45
membrane surface with UV irradiation (inset: digital photograph of
the GO/TiO2 membrane). Reproduced with permission from ref 30.
Wang and co-workers were successful in preparing the large-
Copyright 2017 Elsevier. lateral-size (>200 μm) GO-based NF membrane over a
poly(acrylonitrile) nanofibrous mat (GO/PAN) using the
vacuum filtration method.97 The concentration of the GO
solution could manipulate the thickness of the uniformly
composite over the polymer filtration membrane surface for arranged GO layers. Even at a low external pressure of 1.0 bar,
simultaneous photodegradation as well as water filtration.30 the unique structure allows a high water flux, and further
GO/TiO2 reached a permeate flux of up to 60 LMH, 9 times support of the porous nanofibrous mat also contributes to the
higher than that for the performance of the commercial water flux. Prepared GO/PAN membranes obtained 99%
membrane. In addition, when the membrane is kept under UV rejection for a Congo red dye solution because of the physical
irradiation, TiO2 is excited. It generates highly oxidative sieving and electrostatic repulsion effect. In addition, prepared
species, hydroxyl radicals, and an electron/hole pair, which can GO/PAN membranes were also effective in removing salts,
help in the degradation of organic moieties. GO/TiO2 with a such as 56.7% for Na2SO4 and 9.8% for NaCl. GO nanofilms
dual-performance effect can remove more than 90% of dyes with 2D channels were fabricated over PAN by the vacuum
(acid orange 7, RhB) and humic acid from water under UV filtration method.98 GO/PAN displayed an excellent water flux
irradiation. Hence, GO/TiO2-based membranes possess an of up to 65.1 L m−2 h−1 and a high rejection of 99.8% for
excellent future in the research of water treatment. desalination by pervaporation at 90 °C. The GO/PAN
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Figure 11. UV−vis absorbance spectra of the MO solution after irradiation for 3 h in the presence of (a) Nafion/TiO2 and (b) Nafion/GOSULF.
Reproduced with permission from ref 86. Copyright 2015 Elsevier.

composite membrane could treat even high saline water with a nanoparticles with graphene-based membranes can overcome
salt concentration of up to 100000 ppm. Thus, the hybrid GO the inherent limitation of low water permeability.
membrane could be used for the brackish water desalination.
2.3.3. GO/Nanoparticle Hybrid Membrane. Compared to 3. CONVENTIONAL NANOPARTICLES AND
other nanoparticles, silver (Ag) nanoparticles have shown POLYMERIC MEMBRANES
promising performances in water purification because they
Various conventional membranes such as polymeric metal/
limit the growth of microorganisms such as algae, bacteria, and
metal oxide have been approached for water purification.
fungi.99 Research has focused on inducing its property by
However, their application up to now has been limited to
manufacturing it with a graphene-based membrane in the
laboratory scale because of membrane fouling, high hydro-
development of an antibacterial membrane for wastewater
phobicity, and low flux, which makes researchers more
treatment.
intrigued to overcome the disadvantages. Designing hybrid-
Yang and co-workers developed composite membranes of based membranes based on a polymeric metal/metal oxide
GO/Ag nanoparticles (GO/Ag) and studied the size effect of nanoparticle and a fibrous material could unlock their potential
silver in the NF performance.100 The group studied the application in water purification on a large scale. This section
membrane performance for the rejection of RhB dye by tuning provides an overview of hybrid nanomaterials that can be
the size of Ag nanoparticles (8, 20, and 33 nm) in the incorporated with graphene-based membranes to overcome
membrane matrix. The incorporation of 20 nm of Ag the existing drawbacks of pristine graphene membranes. For
nanoparticles in the GO membrane showed the highest flux instance, GO membranes have low operational time because of
(106.1 L m−2 h−1 bar−1) with 97.73% rejection compared to a hydration effect; however, chemical modification of GO with
the other two sizes of Ag nanoparticles. The results were other nanomaterials reduces the swelling of GO membranes
supported by both the interlayer spacing and defect size of GO. during operation. Additionally, the role of nanoparticle
The interlayer spacing increases with an increase in the incorporation in the development of synergistic properties in
nanoparticle size, and the size of the defects decreases with an polymeric and nanofibrous membranes is discussed briefly.
increase in the size of the Ag nanoparticle. Because of the 3.1. Nanofibrous Membranes. Nanofibrous membranes
solution diffusion effect, the rejection of RhB was inversely with 1D morphology offer specialized characteristics like high
correlated with the feed concentration of the RhB solution. mechanical strength, high aspect ratio, and large surface area,
The rGO/gold (Au)-hybridized membrane observed a similar which could have a potential role in membrane technology like
observation.101 The rGO/Au membrane showed a water flux CNT-based membranes. The availability of a large surface-
of 204.1 L m−2 h−1 bar−1 with 99.79% rejection for the RhB area-to-volume ratio is the key requirement for an efficient
dye solution. In addition to the Ag and Au nanoparticles, silica membrane. The electrospinning technique is the most
is referred to as an excellent host for the membrane matrix common method to design nanofibrous membranes resulting
because of its high thermal and chemical stability.102 in uniform pore size, counting significant characteristics of the
Electrostatic stabilization of the silica surface in an aqueous membranes.104,105 In addition, electrospun nanofibrous mem-
medium facilitates the dispersion of nanoparticles, allowing for branes offer a considerably elevated flux and high rejection
high miscibility in the solution phase. This is experimental rates. The TiO2 nanofiber membrane is designed by the
proof that the GO/SiO2 composite membrane synthesized by electrospinning method with the incorporation of Ag nano-
the vacuum filtration method allows rapid passage to water particle106-degraded methylene blue under solar light radiation.
molecules, where the membrane thickness and permeation In the Ag/TiO2 nanofibers, the Ag nanoparticles were grown
were negatively correlated.103 The prepared GO/SiO 2 on the surface of a nanofiber. The membrane was prepared
composite membrane showed high water permeability from the synthesized Ag/TiO2 nanofiber by simply dipping it
(229.15 L m−2 h−1 bar−1) with an excellent rejection rate of into a surfactant solution, followed by sonication. After that,
99% for the RhB dye solution. From the above-mentioned the suspension was filtered with the help of a vacuum filtration
literature, it is worth exploring whether the potential of setup through a glass filter. The membrane was cleaned with
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distilled water, followed by drying and pressurization. Ag/TiO2 aiding the adsorption of heavy-metal ions.111 (3) The negative
displayed higher permeate flux compared to pure TiO2 and the surface charge of the hybrid membrane attracting positively
P25-deposited membrane, providing the same transmembrane charged metal ions through electrostatic attraction could
pressure (TMP). further promote the adsorption.
Proficient removal of fluoride ion from polluted water 3.2. Polymeric Nanocomposite Membrane. Polymeric
streams by employing a carbon-based hybrid membrane made material has been frequently utilized for membrane fabrication
of amyloid fibrils/ZrO2 nanoparticle (<10 nm) nucleated and because of its excellent chemical and thermal stability, fine
grown in situ over the surface of amyloid fibrils using the CVD control of the pore-forming mechanism, higher flexibility, and
method reported.107 Amyloid fibrils function as a template to low cost.112 Polysulfone (PSf), poly(vinylidene fluoride)
grow the ZrO2 nanoparticle through in situ reaction, forming (PVDF), polyurethane (PU), polyamide, sulfonated poly(ether
ZrO2 nanoparticle-coated amyloid fibrils. Later, a hybrid sulfone) (SPES), poly(ether sulfone) (PES), poly(ethylene
membrane (referred to as CAF-Zr) was synthesized by simply terephthalate) (PET), polyester, poly(acrylonitrile) (PAN),
mixing hybrid nanocolloids along with AC for purification and and poly(tetrafluoroethylene) (PTFE) are majorly investigated
the removal of fluoride ions from polluted water. The presence and fabricated as membranes for wastewater treatment because
of carbon offers a large surface area, generating high of these excellent properties.90,113,114 Among all of the
permeability through the membrane. The hybrid membrane polymers present, PSf possesses the highest mechanical
CAF-Zr exhibited an effective fluoride with a removal strength and maximum resistance to temperature.90,113 Even
efficiency of 95.5% in a wide pH range (2−10). The presence if polymeric membranes comprise these characteristics and
of additional competitive anionic species such as SO42‑/Cl−/ become a preferential choice for membrane fabrication, they
NO3− could cause the adsorption efficiency to vary slightly have certain pitfalls, hindering their efficient performance. The
only at high concentration. A powerful selectivity of CAF-Zr drawbacks faced by polymeric membranes are exposure to
toward fluoride against other competitive anions was achieved biofouling, low fluxes, high hydrophobicity, membrane crack,
with a distribution coefficient Kd of 6820 mL g−1, even 180 pore blocking, and low mechanical strength, which could be
times better than that of commercial ion-exchange resins (IRA- overcome with the incorporation of various nanoparticles or
900) in a wide pH range. The wide-range adsorption capability nanotubes, developing a synergistic effect, strength, selectivity,
of the CAF-Zr membrane was due to the strong affinity of and permeability and enhancing their hydrophilicity.115 The
small-sized ZrO2 nanoparticles. The membrane exhibiting a inclusion of nanoparticles in the vicinity of polymeric
99.5% removal efficiency equally in low (several milligrams per membranes has become a recent trend for the development
liter) and high (up to 200 mg L−1) fluoride concentrations, of membranes. For instance, when PVDF membranes are
representative neutral tap water, and different concentrations incorporated with silica nanoparticles, the temperature
of acidic wastewater was taken as supply source. The resistance of the membrane increases with greater selectivity
membrane was employed with real untreated municipal tap and diffusivity.116 The zinc oxide (ZnO) incorporated chitosan
water (∼2.8 mg L−1) under a nonstop working mode and membrane developed strong mechanical properties with high
revealed that ∼1750 kg of water m−2 of membrane can be antibacterial activity.13 A silica nanoparticle incorporated into
treated while water quality was maintained above the drinking PSf demonstrated an increase in the gas permeability.117 A
threshold standardized by WHO with multiple reusability. A higher porosity, a low rejection in flux, and a pseudo-steady-
facile and efficient hybrid membrane based on metallic 2D state permeability of the PES membranes were achieved by
molybdenum disulfide (MoS2) nanosheets and 1D silk incorporating an aluminum oxide nanoparticle,118 whereas a
nanofibrils (SNF) for water purification was designed.108 silica nanoparticle incorporated into polybenzimidazole
The hybrid membrane acquired a multilayer structure, similar membranes delivered greater selectivity in the gas separation
to shell nacre, with a negative surface charge and sufficient with enhanced the permeability.14
interaction sites, because of which it facilitates a favorable 3.2.1. Incorporation of Iron Oxide Nanoparticles. Iron, the
separation performance for organic dyes and metal ions from most omnipresent and abundantly available element among all
water. The separation efficiency was altered by tuning the feed transition metals in the earth’s crust, is the backbone of
ratio of the two nanomaterials. When the membrane was material research. An iron oxide (FeO) nanoparticle is referred
subjected to filtration, because of the reducing ability of MoS2 to as one of the promising materials for water purification
nanosheets, it reduced the precious metal ions to their because of its high availability, surface area, magnetic
respective nanoparticles, excluding further chemical and properties, catalytic activity, low cost, low or no toxicity, and
thermal treatment. Hence, the hybrid membrane is efficient hydrophilic nature. A PES/FeO composite NF membrane can
for single-step removal and recovery of precious metal ions. be used for the removal of copper.119 The membrane showed
In addition, it displayed outstanding performance for the the highest copper removal (92%) with the presence of 0.1 wt
simultaneous purification and determination of dyes from % FeO. The presence of ethylenediaminetetraacetic acid with
water. The surface and cross-sectional scanning electron PES−FeO displayed the best result at 0.1 wt % FeO. Shahwan
microscopy (SEM) images of the hybrid membrane MoS2/ et al. studied the PSf membrane and achieved low membrane
SNF after filtration along with EDS mappings and the fouling because of the development of biofilms.120 The
adsorption capacities for metal ions confirm that the MoS2/ incorporation of FeO nanoparticles has drastically improvised
SNF hybrid membrane has the adsorption capacity for all six the eradication of hydrophobic contaminants and antifouling
metal ions. The three possible factors responsible in the in seawater treatment. Iron−carbon hybrid materials have been
separation mechanism are as follows: (1) Heavy-metal ions are successfully used for the removal of organic contaminants from
complexed with exposed S atoms on the surface of the hybrid water.121
membrane through soft−soft interaction because of the S− 3.2.2. Incorporation of Silica Nanoparticles. Silica is
Mo−S sandwiched architect of MoS2.109,110 (2) The presence referred as an excellent host because of its thermal and
of different amino acids in SNF forms metal−ligand pairs, chemical stability, large surface area, stable dispersion in an
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 Table 2. Summary of Various Nanoparticle-Incorporated Membranes and Their Performancesa
Water flux
Name of the experiment Materials used Method of preparation (LMH) Rejection Ref
PES membrane enhanced with FeO nanoparticles for copper removal from water: application of new Fe3O4 nanoparticles; nonsolvent-induced phase 41.5 92% Cu 119
functionalized Fe3O4 nanoparticles support PES inversion method
Zirconia-nanofiber-incorporated PSf nanocomposite membrane: toward overcoming the permeance−selectivity ZrO2 nanofibers; support nonsolvent-induced phase 339.3 84% BSA 140
trade-off PSf inversion method
Effect of nano-TiO2 loading in PSf membranes on the removal of pollutant following natural-rubber wastewater nano-TiO2; support PSf nonsolvent-induced phase 2.1 14.03% TDS; 87.88% COD; 99% 141
treatment inversion method turbidity
Preparation of a novel PVC ultrafiltration membrane modified with a Ag/TiO2 nanoparticle with enhanced Ag/TiO2; support PVC nonsolvent-induced phase 58.6 98.6% Lanasol blue 3R dye; 142
hydrophilicity and antibacterial activities inversion method 98.02% BSA
ACS Applied Nano Materials

Novel PVA NF membrane modified with dopamine-coated anatase TiO2 core−shell nanoparticles TiO2 nanoparticle; support nonsolvent-induced phase 27 80% microorganism; 85% sulfate; 143
PVA inversion method 70% chloride
Synthesis of PES/GO/SiO2 mixed matrix membranes for oily wastewater treatment SiO2/GO; support PES nonsolvent-induced phase 2561 30% oily wastewater sample 144
inversion method containing Ca, Mg, and K ions
Biocompatible Fe3O4@SiO2−NH2 nanocomposite as a green nanofiller embedded in PES NF membrane matrix Fe3O4/SiO2−NH2 nonsolvent-induced phase 65 93% Cd(II); 97% MR dye 145
for salts, heavy-metal ion and dye removal: long-term operation and reusability tests nanocomposite; support inversion method
PES
Electrospinning superhydrophobic−superoleophilic PVDF/SiO2 NF membrane for oil−water separation SiO2 nanofibers; support electrospinning method 1857 ± 101 99 ± 0.1% oil−water separation 146
PVDF
Facile immobilization of a Ag nanocluster on a NF membrane for oil−water separation Ag nanocluster; support electrospinning method 447.5 ± 100.3 99 ± 0.1% oil−water separation 135
APAN
PAN NF membrane modified with a Ag/GO composite for a water purification system Ag/GO; support PAN electrospinning method 390 30% bacteria 147
a
[PES = poly(ether sulfone); PSf = polysulfone; PVDF = poly(vinylidene difluoride); PVC = poly(vinyl chloride), PVA = poly(vinyl alcohol); APAN = activated poly(acrylonitrile); PAN =
poly(acrylonitrile); Ag = silver; GO = graphene oxide; Cu = copper; Cd(II) = cadmium(II) cation; Ca = calcium; Mg = magnesium; K = potassium; BSA = bovine serum albumin.

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aqueous medium, and inertness.122 Electrostatic stabilization of have been incorporated with Ag nanoparticles such as
the silica surface in an aqueous medium facilitates nanoparticle polyamide, poly(2-ethyl-2-oxazoline), cellulose acetate, and
dispersion, enabling high miscibility in the solution phase. polyimide to improvise the membrane performance.132−134 Li
Wastewater consisting of oil is difficult to separate using et al. produced a superhydrophobic/superoleophilic NF
polymeric membranes when present on a large scale because membrane by incorporating Ag nanoclusters into activated
the polymeric membranes are easily fouled with oil. Research is poly(acrylonitrile) (APAN) nanofibers.135 The fabricated
ongoing to alter the polymeric membranes so that they can be APAN-Ag membrane displayed a high water contact angle of
employed on a large scale for wastewater treatment containing 162.4 ± 1.9°, a low oil contact angle of 0°, a self-cleaning
oil. The excellent physicochemical stability, oxidation resist- surface-holding water contact angle hysteresis of 3.4 ± 0.9°,
ance, and presence of chlorine makes PSf a good candidate for and a smaller water-adhesion propensity. The synthesized
membrane material. However, its surface energy is low, with APAN-Ag membrane efficiently separated oil/water mixtures
strong hydrophobicity resulting in a weaker antifouling ability. in both hypersaline and different pH media. Zodrowet and co-
Numerous efforts have been made to improvise the hydro- workers reported that the impregnation of 0.9 wt % nAg into
philicity of the membrane,123−125 among which inorganic PSf does not affect the permeability or surface charge of the
oxide doping to a polymer to produce an organic−inorganic membrane. However, the composite membrane showed an
composite membrane solves the issue. A cerium-doped improved hydrophilic property compared to the pristine PSf
nonstoichiometric nanosilica (modified nanosilica) combined membrane with a 10% drop in the contact angle.136 The
with PSf to engineer a new type of composite membrane was asymmetric arrangement of silver-impregnated membranes was
developed.126 The composition of the silica nanoparticle was evident. A change in the membrane structure with the
kept constant at 10 wt % PSf to differentiate the performance impregnation of nAg could not be identified visually. Still, its
and its effect of modified and unmodified silica nanoparticle, presence adversely affected in the amount of growth of
without incorporating nanoparticle in the PSf membranes. The Escherichia coli on the membrane surface after the dilute
addition of nanoparticle enhanced the membrane performance bacteria suspension was filtrated out, which is indicated by the
concerning its permeability, mechanical strength, etc. How- number of colony-forming units per 9.35 cm2 membrane
ever, the concentration of the nanoparticle should be limited coupons.
because increasing the weight of the nanoparticle in the Even the incorporation of a Ag nanoparticle into the
membrane could be harmful to membrane activity. The polymeric membrane exhibits a huge number of advantages,
average TMP is 0.05 MPa; a collection of permeates were but researches still hesitate to use it in wastewater treatment
examined and undertaken less than 90 min after the operation. because of its high reactivity, which is a nanoparticle
A comparative study of the separation efficiency was characteristic. The presence of excessive Ag nanoparticles can
performed for membranes synthesized with different casting be an environmental and health risk.137 When Ag nanoparticles
solutions. When a modified nanosilica/PSF composite are incorporated in the polymeric membrane for a drinking
membrane was employed, the permeate flux flattened out water filtration system, it may cause leaching of Ag nano-
after 90 min at 80 L m−2 h−1 and the pure water flux leveled off particles into the drinking water. The leaching out of Ag
after 90 min at 120 L m−2 h−1 during a oil−water separation nanoparticles could happen because of an improper impreg-
procedure. By the addition of a modified inorganic oxide nation technique or any physical damage. Further, exposure to
nanoparticle with the help of novel cerium-doped non- a high concentration of Ag for a longer period could result in
stoichiometric nanosilica, the tensile strength could be diseases like argyria, a blue-gray discoloration of the skin and
improved to a certain degree. Reports propose that other organs.138 Reports also depict that Ag nanoparticles
intermolecular forces between the polymeric chain and could damage DNA and apoptosis in mouse embryonic stem
incorporated inorganic oxide nanoparticles dispersed uniformly cells and fibroblasts.139 A list of various studies and their
in PSf partly check the polymeric chain, resulting in sequential performances is tabulated in Table 2 for nanoparticle-
improvement of the membrane tensile strength. In addition, incorporated membranes.
the inorganic oxides are very well packed by polymeric chains
twisting mutually, which further enhances the membrane’s 4. CURRENT CHALLENGES AND FUTURE RESEARCH
tensile strength.127 The hydrophilicity of the membrane is DIRECTIONS
enhanced with the doping of an inorganic oxide nanoparticle The graphene-based membranes for wastewater treatment
because of the presence of surface hydrophilic hydroxide have been successfully synthesized using different techniques
radicals on the inorganic oxide nanoparticle.128 such as the casting/coating, LBL self-assembly, or vacuum/
3.2.3. Incorporation of Ag Nanoparticles. Silver has been pressure-assisted methods. However, certain challenges prevail
most remarkable for the design of tableware and coinage from in continuous research and studies. In the GO membranes,
ancient times because of its high resistance to corrosion, low reduction of the interlayer spacing and maintenance of the
toxicity, and antibacterial property.129 Moreover, Ag nano- structural stability at a particular level for the exclusion of
particles have shown a promising performance in water small-sized ions are the major challenges. Further, maintaining
purification because it restricts the growth of microorganisms the same spacing without swelling of the GO membranes when
like algae, bacteria, and fungi. Research has been focused on dispersed in the aqueous medium is another concern that
inducing its property in the growth of an antibacterial could limit its potential application for ion filtration.
membrane for wastewater treatment by its fabrication with a Current efforts for designing the ultrathin separation layer of
polymer membrane. The interaction of silver with sulfur or GO membranes enhance its application scale from water
phosphorus, mainly with thiol groups (-SH), which is present separation to organic solvent NF, including gas separation. In
in cysteine.130 Ag nanoparticle association with the thiol group the pressure filtration method, effective desalination of water
destroys bacterial proteins, dimerizes DNA, and affects the via GO membranes is hard to achieve, claiming a requirement
transport chain of electrons.131 Various polymer membranes of subnanosized channels in the GO membrane structure.
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Hence, the pore channels of GO membranes should be 5. SUMMARY

carefully prepared, so that they can restrict the passage for In this review, we explicitly discuss the achievements of
small-sized ions. Reproduction of GO nanoporous membranes graphene-based membranes. The rapid interest and research
revealed that they allow fast convective water flow through the achievements have made graphene membranes the key
channels as opposed to the slower solution-diffusion water material for the water treatment process. Here, we highlight
transport mechanism in RO membranes. Significant progress various approaches in the development of graphene-based
has been made on the separation mechanisms of graphene- membranes, from fabrication techniques to functionalization
based membranes, and their great potential for liquid and gas and hybridizing methods. The GO separation mechanism and
separation applications has been demonstrated. However, there transport channels within the membranes, including size
are a few significant challenges before graphene-based exclusion, Donnan exclusion, and adsorption, have been
membranes are completely commercialized. discussed briefly. Considerable growth in the design of
(a) First, the graphene-based membranes’ long-term stability CNT-based membranes (VA-CNT, MM-CNT, HA-CNT,
remains a major concern. For practical applications, the testing and CNT-BP) offers excellent achievement in the membrane
period for the stability of graphene-based membranes is only characteristic, selectivity, and performance, with its potential
from several hours to a few days, which is far below the application ranging from liquid separation to gas separation.
duration for industrial applications. The long-term stability of Furthermore, other conventional membranes comprising
the graphene-based membranes needs to be further studied. polymeric materials (PSf, PAA, APAN, and PVDF) and
(b) Second, graphene-based membranes must be resilient metal/metal oxide nanoparticles such as TiO2, FeO, silica, Ag,
toward backwash and chemical cleaning because these are and ZnO, have been discussed. However, the pristine
applied to overcome membrane fouling. However, there are polymeric membrane performance limits their industrial
still limited graphene-based membranes that can withstand application. Alteration of the polymeric membrane material
backwashing and chemical cleaning. with the incorporation of a nanoparticle-forming complex
(c) Finally, it is still challenging to stabilize the effective offers certain advantages such as high selectivity, high diffusion
separation of graphene-based membranes in liquid separations. rate, permeability, better tensile strength, low fouling, and
It has been reported that the d spacing of graphene nanosheets resistance to high temperature and pressure compared to pure
changes during operation because of the hydration effect polymeric materials. Nevertheless, these materials are far from
generated by water molecules. the results of graphene-based membranes for water purifica-
Further, CNT membranes, have some inherent limitations tion, and thus further research and understanding are needed
such as poor dispersion, high cost, large-scale production, for advanced membrane materials.

■
functionalization, exact loading of material, preservation of
alignment, and integration of CNT materials with support is AUTHOR INFORMATION
still needed to outshine. A chemical oxidation process is
Corresponding Authors
followed for the functionalization of CNTs that could enhance
the adsorption capacity and dispersity of CNTs. However, this Ali Altaee − Centre for Green Technology, School of Civil and
requires an extreme reaction environment that could result in Environmental Engineering, University of Technology Sydney,
the production of chemical waste. Further, it ruptures the Sydney, New South Wales 2007, Australia;
sidewalls and tips of CNTs that could affect the structural Email: [email protected]
Akshaya K. Samal − Centre for Nano and Material Sciences,
stability as well as the electrical and thermal properties.
Jain University, Ramanagara, Bangalore 562112, India;
Hence, studies are needed to develop a novel approach for
orcid.org/0000-0002-7623-3711; Email: s.akshaya@
facile synthesis of graphene-based membranes that could be
jainuniversity.ac.in
inexpensive and large-scale productive. A deeper under-
standing of structural properties and mechanisms for the Authors
elimination of water pollutants should be further pursued. Also, Prangya Bhol − Centre for Nano and Material Sciences, Jain
the toxicity of the membrane should be studied thoroughly to University, Ramanagara, Bangalore 562112, India
avoid hazardous issues. Real-time application and utilization of Sudesh Yadav − Centre for Green Technology, School of Civil
graphene-based membranes for water purification can be and Environmental Engineering, University of Technology
achieved with future research. Sydney, Sydney, New South Wales 2007, Australia
(a) Functionalization of nanoparticles or the design of Manav Saxena − Centre for Nano and Material Sciences, Jain
hybrid mixed-matrix membranes for enhancing water treat- University, Ramanagara, Bangalore 562112, India
ment performance. Pramila Kumari Misra − Centre of Studies in Surface Science
(b) Adoption of novel routes for utilizing renewable sources and Technology, School of Chemistry, Sambalpur University,
for the generation of cost-effective graphene-based membranes. Burla, Odisha 768019, India
(c) Integration of conventional techniques with graphene-
Complete contact information is available at:
based membranes for advanced water treatment processes.
https://pubs.acs.org/10.1021/acsanm.0c03439
It is necessary to develop a method with scalable and
reproducible membrane fabrication. Membranes with accurate
Author Contributions
material loading is also a challenge and can be overcome with a †
proper strategy that can integrate the graphene materials with P.B. and S.Y. contributed equally. The review has been
other matrixes or nanoparticles, developing a synergistic effect written through the contributions of all authors. All authors
and high performance in the water treatment process. have approved the final version of the review.
Overcoming these drawbacks will make graphene a potential Notes
candidate for water and wastewater treatment. The authors declare no competing financial interest.
3288 https://doi.org/10.1021/acsanm.0c03439
ACS Appl. Nano Mater. 2021, 4, 3274−3293
ACS Applied Nano Materials

■
www.acsanm.org Review

ACKNOWLEDGMENTS (19) Hung, W.-S.; Tsou, C.-H.; De Guzman, M.; An, Q.-F.; Liu, Y.-
L.; Zhang, Y.-M.; Hu, C.-C.; Lee, K.-R.; Lai, J.-Y. Cross-linking with
P.B. and A.K.S. are grateful to SERB, New Delhi, India, for diamine monomers to prepare composite graphene oxide-framework
funding to conduct the research (Grant CRG/2018/003533). membranes with varying d-spacing. Chem. Mater. 2014, 26 (9),
S.Y. is grateful for the scholarship support from University of 2983−2990.
Technology Sydney under the UTS President’s Scholarship (20) Panchakarla, L.; Subrahmanyam, K.; Saha, S.; Govindaraj, A.;
and the International Research Scholarship (IRP). Krishnamurthy, H.; Waghmare, U.; Rao, C. Synthesis, structure, and

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properties of boron-and nitrogen-doped graphene. Adv. Mater. 2009,
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