polymers

Review
Advanced Polymeric Nanocomposite Membranes for Water and
Wastewater Treatment: A Comprehensive Review
Abhispa Sahu 1, * , Raghav Dosi 2 , Carly Kwiatkowski 2 , Stephen Schmal 3 and Jordan C. Poler 2, *

1 American Nano, LLC, 2011 Muddy Creek Road, Clemmons, NC 27012, USA
2 Department of Chemistry, University of North Carolina at Charlotte, 9201 University City Blvd,
Charlotte, NC 28223, USA
3 Goulston Technologies, 700 N Johnston St, Monroe, NC 28110, USA
* Correspondence: [email protected] (A.S.); [email protected] (J.C.P.)

Abstract: Nanomaterials have been extensively used in polymer nanocomposite membranes due
to the inclusion of unique features that enhance water and wastewater treatment performance.
Compared to the pristine membranes, the incorporation of nanomodifiers not only improves mem-
brane performance (water permeability, salt rejection, contaminant removal, selectivity), but also
the intrinsic properties (hydrophilicity, porosity, antifouling properties, antimicrobial properties,
mechanical, thermal, and chemical stability) of these membranes. This review focuses on appli-
cations of different types of nanomaterials: zero-dimensional (metal/metal oxide nanoparticles),
one-dimensional (carbon nanotubes), two-dimensional (graphene and associated structures), and
three-dimensional (zeolites and associated frameworks) nanomaterials combined with polymers
towards novel polymeric nanocomposites for water and wastewater treatment applications. This
review will show that combinations of nanomaterials and polymers impart enhanced features into
the pristine membrane; however, the underlying issues associated with the modification processes
and environmental impact of these membranes are less obvious. This review also highlights the
utility of computational methods toward understanding the structural and functional properties of
Citation: Sahu, A.; Dosi, R.; the membranes. Here, we highlight the fabrication methods, advantages, challenges, environmental
Kwiatkowski, C.; Schmal, S.; Poler, impact, and future scope of these advanced polymeric nanocomposite membrane based systems for
J.C. Advanced Polymeric water and wastewater treatment applications.
Nanocomposite Membranes for
Water and Wastewater Treatment: A Keywords: polymer nanocomposites; water treatment; inorganic nanoparticles; desalination;
Comprehensive Review. Polymers computational studies; biopolymers
2023, 15, 540. https://doi.org/
10.3390/polym15030540

Academic Editors: Mariia E.

Dmitrenko, Anastasia V. Penkova 1. Introduction
and Lusi Zou Water is essential for sustainable development, energy and food production, healthy
Received: 23 December 2022
ecosystems, and, of course, all life. Industrialization is at the core of urbanization and
Revised: 13 January 2023 significantly contributes to the advancement of human welfare [1]. However, population
Accepted: 16 January 2023 growth, industrialization, and socio-economic growth have led to anthropomorphic cli-
Published: 20 January 2023 mate change and pollution, and thereby the deterioration of water quality, especially in
developing countries. One-third of the world’s population is suffering from scarcity of safe
drinking water. This figure is expected to rise to two-thirds by 2025 [2,3]. Hence, one of the
utmost global challenges is meeting the demand for safe drinking water [4].
Copyright: © 2023 by the authors. Rapid industrial growth has exacerbated the production and widespread fouling of
Licensee MDPI, Basel, Switzerland. natural water resources [5]. These contaminants are of emerging concern because they are
This article is an open access article perceived as potential threats to human life and the environment [5,6]. Different classes
distributed under the terms and
of emerging contaminants, their source of origin, and their adverse health effects are
conditions of the Creative Commons
listed in Table 1. Emerging contaminants can be primarily classified as organic, inorganic,
Attribution (CC BY) license (https://
microbial, perfluoroalkylated, and radioactive substances [3,6–10]. They do not degrade or
creativecommons.org/licenses/by/
hydrolyze easily and are persistent in the environment, resulting in bioaccumulation [6].
4.0/).

Polymers 2023, 15, 540. https://doi.org/10.3390/polym15030540 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 540 2 of 49

Even though the acute nature of any adverse health effects will depend on an individual’s
susceptibility and the mode of contact with the body, the US EPA has established maximum
concentration levels (MCLs) for these contaminants in drinking water. For example, heavy
metals include cadmium with an MCL of 5 parts per billion (ppb), antimony with 6 ppb,
lead with 15 ppb, and uranium MCL with 30 ppb [11–13]. Pesticides such as toxaphene and
alachlor have an MCL of just 3 and 2 ppb, respectively [12], and many perfluoroalkylated
compounds have MCL below 1 ppb, such as perfluorooctanoic acid and perfluorooctane
sulfonate (both individually and combined) at less than 70 parts per trillion (ppt) [14].
The US EPA has recently announced that there is no safe level for the perfluoroalkylated
compounds. Moreover, the lowest predicted no effect concentration (LPNEC) for a few
contaminants in freshwater include 20 ppt for ciprofloxacin (antibiotic), 18 ppt for estrone
(hormones) [9], and 560 ppt for 4 MBC (sunscreen) [15]. Given the potential health risks
and low MCLs associated with these pervasive chemicals (shown in Table 1), there has been
significant ongoing efforts to understand the occurrence and health consequences of these
contaminants. This review will discuss many of the developing robust water purification
technologies for the production of safe and clean drinking water. In addition to removing
anthropomorphic contaminants, we will discuss various methods to remove minerals from
seawater and brackish water. Desalination technologies that treat natural water resources
have evolved tremendously in recent decades to support urban and industrial development
in areas with limited water supply and/or high transportation or development costs [16].

Table 1. Different types of contaminants and their associated adverse health effects, examples, and
maximum concentration levels.

Examples and Their Maximum

Impact on Human Health
Contaminants Generation Source Concentration Levels
or Ecology
(Parts per Billion (ppb))
Pesticides, pharmaceuticals,
natural organic matter,
Mutagenicity, Dibromochloropropane—0.2,
disinfection byproducts,
carcinogenicity [17], simazine—4 [9], Dioxin
endocrine disrupting
Organic bladder cancer, (2,3,7,8-TCDD)—0.00003,
chemicals, hormones and
developmental issues, Hexachlorocyclopentadiene—50,
steroids, personal care
increased birth defects [18] Hexachlorobenzene—1 [19]
products, flame retardants,
plasticizers [6,10]
Byproduct of metal mining, Toxic effect on aquatic flora
smelting, fossil fuel and fauna, catharsis, Arsenic—10, cadmium—5,
Inorganic (acids, salts,
combustion, mineral deposits, congenital malformation, lead —15 [11], Mercury—2,
heavy metals)
anerobic groundwater, increased cancer risk, cyanide —200 [13]
soil erosion cardiovascular effects [20]
Human and animal fecal Typhoid, cholera, diarrhea,
Microbial (bacteria,
wastes, Fertilizer, damage to liver, skin, nervous E. coli—0 [22]
virus, algae, protozoa)
livestock, sewage system, stomach cramps [21]
Adversely affect growth, birth
Firefighting foams, lubricants,
weight, fertility disorders, Perfluorooctane sulfonate,
Perfluoroalkylated coating additives, cookware,
early menopause, thyroid perflourooctanoic acid—0.07 (both
compounds food packaging, textile
malfunction, and individually and combined) [14]
industry, paper packaging [8]
carcinogenesis [7]
DNA damage, osteosarcoma
incidence, leukemia, stomach
Mining and processing of
Radioactive substances cancer, urinary cancer, Uranium (U)—30 [11,13]
radioactive minerals
biomarkers of renal (tubular)
damage [23]

Membrane technology has become indispensable in numerous industries such as

food [24], pharmacy [25], textile [26], petroleum products [27], chemicals [28], lithium
Polymers 2023, 15, 540 3 of 49

ion batteries [29], fuel cells [30], gas separation [31], and wastewater and drinking water
treatment systems [32,33]. Compared to all other conventional water treatment methods,
membrane technologies offer affordable solutions that support excellent contaminant re-
jection, low energy consumption, and easy availability of raw materials [34,35]. Over
the past two decades, synthetic membranes have played an integral role in industrial
and domestic applications, and have replaced commercially available cellulose-derived
membranes (cellulose diacetate, cellulose triacetate, and regenerated cellulose) due to their
high tolerance to stressful conditions [33,36,37]. Synthetic membranes can be fabricated
using organic materials (polymers) or inorganic materials (metals, oxides, and ceramics).
Membrane technology has the flexibility of employing a wide range of materials based
on material type (ceramic: zirconia, titania, silica, alumina, etc.; metal: silver, palladium,
copper, etc.; polymer: polyvinylidene difluoride (PVDF), polyether sulfone (PES), polysul-
fone (PSf), polyvinyl alcohol (PVA), polyetratfluoroethylene (PTFE), polypropylene (PP),
polyamide (PA), polyimide, poly(1-vinylpyrrolidone) (PVP), polyvinyl chloride (PVC),
polyacrylonitrile (PAN), etc.) and pressure driven membrane separation processes (micro-
filtration (pore size: 50–500 nm), ultrafiltration (pore size: 2–50 nm), nanofiltration (pore
size ≤ 2 nm), reverse osmosis (pore size: 0.3–0.6 nm), and forward osmosis (pore size:
0.3–0.6 nm)) [3,32,35,37–43].
Inorganic and organic materials bring their own benefits and challenges in the de-
velopment of synthetic membranes. Inorganic membranes have exceptional mechanical
strength, high durability, and high tolerance to chemical oxidation or extremes of pH,
but also have high manufacturing cost and little to no control on pore size distribution,
which make them less likely to be suitable for industrial use [1,44,45]. Polymer (or organic)
membranes are widely used technologies in water treatment due to their high degree of
control over pore size distribution, high flexibility in operating conditions, ease of synthesis,
and cost effectiveness [1,44]. These polymeric membranes are commercially available with
differentiated porosities that can be tuned for applications such as suspended solids, oil
emulsions and microbe removal (microfiltration (MF); for colloidal solids, viruses, hu-
mics, proteins/polysaccharides removal (ultrafiltration, UF); for heavy metals, dissolved
organic matter, common pharmaceuticals or pesticides removal (nanofiltration, NF); for
desalination and ultrapure water production (reverse osmosis, RO and forward osmosis
(FO)) [37,46,47]. These targeted functional systems are fabricated as thin-film composite
(TFC) membranes that have been widely used in membrane-based water purification
systems [48]. TFC membranes are comprised of a non-woven fabric support layer on
which a porous intermediate polymer (PES or PSf) layer (~50 nm) is combined with a
thin, highly crosslinked dense PA layer (<200 nm) [35,49,50]. The top epidermal layer
provides selectivity and/or separation while the porous substrate layer that is perme-
able to water and dissolved solute particles provides mechanical strength [32,51]. These
membranes exhibit better salt rejection, higher water flux or permeability, and higher
stability (chemical, mechanical and thermal) compared to commercially available cellulose-
based membranes [50–53]. PSf and PES are the most commonly used materials for UF
applications and are used as the standard base substrates for NF and RO composite mem-
branes [32]. PP and PVDF are more commonly used for MF membranes [37,41]. However,
there are key problems associated with TFC membranes. These membranes are prone to
fouling, are highly hydrophobic, have low chlorine resistance, low mechanical strength, and
demonstrate an inherent tradeoff between water flux and solute selectivity [4,33,35,44,54].
Apart from these, RO systems have a relatively high energy demand to desalinate feedwa-
ter [55,56]. Because these TFC have some inadequacies in achieving long-term viability and
cost-effective membrane models, the incorporation of nanomaterials has emerged as an
effective approach to overcome these application challenges.
When nanomaterials are incorporated in the epidermal or porous intermediate layer
or substrate/support, it produces polymer nanocomposite membranes. Compared to
conventional TFC membranes, these nanocomposite membranes offer unique morphologies
that overcome the limitations of pristine polymer membranes, leading to better performance
Polymers 2023, 15, 540 4 of 49

and less energy demand. There are two ways of incorporating inorganic nanoparticles (NPs)
into a polymer matrix. This can be either done by multilayer coating of NPs on polymer
substrate or layer (thin-film nanocomposite membrane (TFNC)) [57,58] or dispersing NPs
into a polymer blend, which forms into a cast (blended nanocomposite membranes) [39,59].
Blending can be achieved via phase inversion (PI) method, which is classified into four
different types, and one of the common types used in fabrication is the non-solvent-induced
phase separation (NIPS) method [39,60]. Fabrication of polymer membrane using NIPS has
been shown in Figure 1. NPs are added to the solvent along with other additives and PSf
(or any other polymer). This dope solution is casted on a glass plate with a casting blade set
at a known gate height which is immediately transferred to a coagulation bath for polymer
thin film to initiate the PI process. The membrane is peeled off the glass plate and kept
in the bath to complete the PI process. By addition of hydrophilic fillers like NPs, there is
a faster rate of organic solvent and non-solvent (water) exchange during the PI process,
which leads to the diffusion of water from the water coagulation bath to polymer thin film,
and the dissolution of walls between inner macrovoids and cavities leading to cavities
of wider pores/voids and higher porosity (shown in Figure 1a) [61,62]. NPs can also be
impregnated in the active epidermal layer (mainly PA) on the substrate during interfacial
polymerization (IP) [63] or can be integrated as an intermediate layer between porous PSf
substrate and semidense PA layer (shown in Figure 1b) [64]. This PA layer is prepared
through the reaction between trimesoyl chloride (TMC) solution and m-phenylenediamine
(MPD) solution during the IP process. NPs are added to either aqueous MPD or organic
TMC phase depending on the hydrophilicity of NPs [65]. Multilayer coating of NPs on the
substrate can be done by dip coating or layer-by-layer (LBL) deposition [66]. NPs loaded
polymer sol–gel can also be electrospun at a high voltage into a nanofibrous membrane (shown
in Figure 1f) [67–69]. There is the possibility of pressure driven membrane deposition of a
dispersion of nanomaterials and the polymer [70,71]. Alternatively, NPs can be chemically
cross linked to the polymer substrate [72,73], NPs can be grown in situ on the polymer
surface [68], or the polymer can be covalently attached to the nanomaterials surface [74–76].
TFNCs are typically thin films of NPs coated on a polymer layer or substrate by dip coating,
self-assembly, pressure-driven deposition, and other related techniques [39]. Mixed matrix
membranes (MMMs) are membranes in which NPs are embedded as a dispersed phase
into a polymer matrix, which can be achieved using techniques such as PI, electrospinning,
crosslinking, LBL deposition, etc. [77–82]. This review will mostly focus on nanomaterials
incorporated
Polymers 2023, 15, x FORin the
PEER polymer substrate, but a few examples of other possibilities shall
REVIEW 5 of be
50
discussed as well.

Figure 1. Various methods of integrating nanoparticles with polymer to form polymer nanocompo-
Figure 1. Various methods of integrating nanoparticles with polymer to form polymer nanocomposite
site membranes: (a) Schematic representation of one of the phase inversion methods (non-solvent-
induced phase separation) for fabrication of polysulfone (PSf) layer. (b) Integration of nanoparticles
either in the polyamide (PA) layer or as a thin layer at the bottom of the PA layer on top of PSf layer
in nanocomposite membrane using interfacial polymerization method (MPD—m-phenylenedia-
mine, TMC—trimesoyl chloride). (c) Short polymer strands grafted on a nanoparticle surface or na-
noparticles grafted from the polymer membrane. (d) Pressure driven filtration of dispersion/solu-
tion of polymer and nanoparticles (polymer grafted nanoparticles example in this case). (e) Dip
coating of polymeric membrane in a dispersion/solution containing nanoparticles. (f) Electrospin-
Polymers 2023, 15, 540 5 of 49

membranes: (a) Schematic representation of one of the phase inversion methods (non-solvent-induced
phase separation) for fabrication of polysulfone (PSf) layer. (b) Integration of nanoparticles either
in the polyamide (PA) layer or as a thin layer at the bottom of the PA layer on top of PSf layer in
nanocomposite membrane using interfacial polymerization method (MPD—m-phenylenediamine,
TMC—trimesoyl chloride). (c) Short polymer strands grafted on a nanoparticle surface or nanopar-
ticles grafted from the polymer membrane. (d) Pressure driven filtration of dispersion/solution
of polymer and nanoparticles (polymer grafted nanoparticles example in this case). (e) Dip coat-
ing of polymeric membrane in a dispersion/solution containing nanoparticles. (f) Electrospin-
ning of nanoparticles added in sol–gel (g). Layer-by-layer assembly of polymer and nanoparticles
(NPs—nanoparticles, NWs—nanowires), [83], © American Chemical Society, 2008. For easy interpre-
tation, spherical shapes are used for nanoparticles in most of the figures.

NPs differ from their larger bulk materials in that their size, shape, and dimension-
ality affect their properties and performance as a material. Specifically, when their size
is reduced, the particles have extremely high specific surface area and surface-area-to-
volume ratios. In a nanomaterial, at least one of the dimensions is in the nanoscale range of
1–100 nm. The nanomaterials are classified into zero-dimensional (0D), one-dimensional
(1D), two-dimensional (2D), and three-dimensional (3D) nanomaterials. In 0D nanomateri-
als, all three dimensions are at the nanoscale. Examples include quantum dots, core shell
NPs, nanospheres, etc. In 1D nanomaterials, two dimensions are at the nanoscale, giving
the structures a rod like shape. Examples include nanowires, nanofibers, and nanotubes.
In 2D nanomaterials, one dimension is at the nanoscale, giving the structures a sheet-like
topology, e.g., graphene sheets. The 3D nanomaterials are not confined to the nanoscale in
any dimension, which can include polycrystals, bundles of nanowires or nanotubes, and
nanoporous solids. Examples include graphite, dendrimers, liposome, etc. [84]. For illustra-
tion, various dimensionalities of carbon allotropes are shown in Figure 2. The nanomaterial
properties can be fine-tuned as desired by precisely controlling the size, shape, synthesis
conditions, and necessary functionalization.
Additives like PVP and poly(ethylene glycol) (PEG) play important roles in membrane
modification. They act as pore-forming agents and modify hydrophilicity and antifoul-
ing properties. However, dissolution or extrusion of homopolymer additives can lead
to the deterioration of properties and the weakening of membrane performance. In this
case, amphiphilic copolymers come to the rescue and show better compatibility, but these
copolymers require costly and complex synthesis, making it difficult to achieve large scale
production [39,86]. Maggay et al. investigated the amphiphilic nature of the copolymer of
styrene and ethylene glycol methacrylate that was used to modify the PVDF membrane.
It was found that the increase of the hydrophilic part led to the decline in anchoring sites,
which led to a compromise in stability; the increase of the hydrophobic part led to the
decrease of the antifouling property and increased protein adsorption on the surface. In
addition to this, fine tuning of chain lengths of copolymer was required as well [87]. There
are several reasons why there has been great interest in the development of polymeric
nanocomposite membranes incorporating nanomaterials in drinking water and wastewater
treatment systems. First, the incorporation of nanomaterials can implement extraordi-
nary variations in polymeric nanocomposite properties such as permeability, selectivity,
hydrophilicity, conductivity, magnetism, mechanical strength, thermal stability, and an-
timicrobial properties [35,41,44,88–90]. Second, there has always been a threat of NPs
leaching out into the environment, whereas their incorporation into a hybrid polymer
nanocomposite can mitigate the possibility of environmental discharge due to encapsula-
tion [4,5,91]. Third, fouling in pristine polymeric membranes has been a serious problem.
It is a well-known fact that foulants get adsorbed on the membrane surface due to van der
Waals interactions, hydrogen bonding, and hydrophobic interactions [35]. Modification of
the surface charge of polymeric membranes with hydrophilic components helps prevent
or reduce undesirable foulant interactions and boost membrane longevity. For instance,
Polymers 2023, 15, 540 6 of 49

modification of PVDF membranes has been performed by grafting or blending amphiphilic

copolymers [92–94], introducing hydrophilic components [95–97], or by incorporating NPs
in the PVDF substrate during PI fabrication methods [60,61,98]. Apart from this, antifouling
properties can also be enhanced with NPs that introduce photocatalytic, self-cleaning, and
photodegradable properties [35]. In addition, NPs with tunable porosities impart enhanced
selective separation in these MMMs [99]. Thus, the addition of NPs has been beneficial
for the long-term usage of polymer nanocomposites due to reduced membrane fouling.
Because the fabrication of NPs often requires toxic chemicals, there has been ongoing
Polymers 2023, 15, x FOR PEER REVIEW 6 of 50
research efforts in the implementation of sustainable methods to facilitate the widespread
use of nanomaterials in water treatment [35].

Figure2.2.Classification
Figure Classification of nanomaterials
of nanomaterials of carbon
of carbon allotropes
allotropes based
based on their on their dimensionality.
dimensionality. Adapted
Adapted
with with permission
permission from Gaurfrom
et al. Gaur et al. [85]. (2021)
[85]. Copyright Copyright
MPDI.(2021) MPDI.

ItAdditives
is important liketoPVP
haveandan optimum polymer/NP
poly(ethylene interphase/adhesion
glycol) (PEG) play importantregion roles into mem-
over-
come
braneagglomeration,
modification. They whichact is one of the major challenges
as pore-forming agents andinmodify
the homogenous
hydrophilicitydispersion of
and anti-
NPs in a properties.
fouling polymer blend. Agglomeration
However, dissolutionnot or only affects
extrusion ofthe performanceadditives
homopolymer and mechanical
can lead
properties, but weak of
to the deterioration adhesion
properties between
and thetheweakening
polymer and of the agglomerated
membrane NPs canInlead
performance. this
to
case, amphiphilic copolymers come to the rescue and show better compatibility,[100–102].
composite failure due to the concentration of exerted force on weak spots but these
Ashraf et al. require
copolymers showedcostlythat two grams ofsynthesis,
and complex well dispersed
makingand isolatedto10
it difficult nm radius
achieve large NPs
scale
can produce [39,86].
a remarkable interfacial area of 250the 2
m amphiphilic
within a polymer
production Maggay et al. investigated naturematrix [103]. When
of the copolymer of
particles
styrene and come in contact,
ethylene glycol they interact through
methacrylate that wasvan dertoWaals
used modify (vdW) attractive
the PVDF forces.
membrane.
The second
It was found interaction is electric
that the increase double
of the layer (EDL)
hydrophilic repulsion,
part led which in
to the decline arises due tosites,
anchoring the
charged surface and surrounding counter ions and falls off exponentially
which led to a compromise in stability; the increase of the hydrophobic part led to the with interpar-
ticle distance.
decrease of theDerjaguin–Landau–Verwey–Overbeek
antifouling property and increased protein (DLVO) theory combines
adsorption the vdW
on the surface. In
attractive force and the EDL repulsive force to understand the overall
addition to this, fine tuning of chain lengths of copolymer was required as well [87]. interactions between
There
the
areNPs within
several the polymer
reasons why there matrix
has [104,105].
been greatThe otherin
interest non-DLVO
the developmentforces that
of influence
polymeric
aggregation are hydration forces and hydrophobic interactions.
nanocomposite membranes incorporating nanomaterials in drinking water It is the interplay betweenand
these short-range thermodynamic interactions that determines the
wastewater treatment systems. First, the incorporation of nanomaterials can implement aggregation of colloidal
extraordinary variations in polymeric nanocomposite properties such as permeability, se-
lectivity, hydrophilicity, conductivity, magnetism, mechanical strength, thermal stability,
and antimicrobial properties [35,41,44,88-90]. Second, there has always been a threat of
NPs leaching out into the environment, whereas their incorporation into a hybrid polymer
Polymers 2023, 15, 540 7 of 49

particles. However, as the nanofiller concentration increases, there is a dominance of strong

vdW forces that result in irreversible agglomeration [106]. External factors, such as the
solvent removal process, add new forces such as capillary action that can promote NP
aggregation as well [105]. Liu et al. performed molecular dynamics (MD) simulations and
demonstrated that a homogeneous dispersion of nanofillers is achieved at the intermediate
interphase interaction, which is contrary to conventional theories [107]. In this review, we
have cited several filler-polymer combinations where an optimum concentration resulted in
best interphase compatibility, properties, and performance, beyond which the performance
deteriorated. Hence, it is crucial to manipulate the particles and minimize the colloidal ag-
glomeration through methods such as mechanical agitation (like ultrasonication [108–111]),
surface modification/functionalization to modify surface zeta potential [112], optimization
of the incorporation procedure [113], etc.
TFC membranes are state-of-the-art and further progress has been made in their
fabrication by introducing nanomaterials to formulate TFNC membranes [48]. TFNC
membranes were first reported by Joeng et al. (2007), where the authors developed the
first generation of MMMs by embedding NaA zeolite NPs in PA thin films interfacially
polymerized on a PSf support. These RO membranes demonstrated a two-fold increase in
water flux (9.37 → 16.96 L m−2 h−1 ) and did not affect the solute rejection (93.9%, 2000 ppm
feed concentration, 12.4 bar pressure), making them comparable to commercial RO mem-
branes [114]. This paved the way for the exploration of nanomaterials to generate unique
morphologies for preferential water flow and excellent salt rejection. Incorporation of
NPs in TFNC contributes to the enhancement of membrane properties such as enhanced
hydrophilicity, water permeability/flux, excellent salt rejection, removal of organic and in-
organic contaminants, and enhanced resistance to chlorine and fouling [41,115–118]. TFNC
polymeric membranes have drawn considerable attention in the past decade (as shown
in Figure 3). This review focuses on the key ongoing advances in nanomaterial-modified
Polymers 2023, 15, x FOR PEER REVIEW 8 of 50
polymeric thin-film membranes that—more specifically—benefit water and wastewater
treatment technologies.

Figure 3. Research impact of thin-film polymeric nanocomposites analyzed using web of science
Figure 3. Research impact of thin-film polymeric nanocomposites analyzed using web of science
database for the past decade.
database for the past decade.
We have further divided this review, focusing specifically on metal- or metal-oxide-
We carbon-nanostructures-based,
based, have further divided this review, focusing specifically on metal-
zeolite-framework-based, or metal-oxide-
and environmentally
based, carbon-nanostructures-based, zeolite-framework-based, and environmentally
sustainable-materials-based polymer nanocomposite membranes. These nanocompos- sus-
tainable-materials-based polymer nanocomposite
ite membranes will be systematically evaluated for membranes.
new properties These nanocomposite
and enhancement of
membranes will be systematically evaluated for new properties and enhancement
existing properties that benefit from the introduction of NPs. The influence of different of ex-
isting
typesproperties thatconcentration,
of NPs, their benefit from the introduction
their of NPs. The
loading positions, influence
their of different
effect on types
morphologies,
of NPs, their concentration, their loading positions, their effect on morphologies, factors
controlling the performance (hydrophilicity, antifouling, addition of surface charge, po-
rosity, thermal, mechanical strength, change in surface roughness), and performances
(permeability, selectivity/separation, rejection) will be comprehensively evaluated. This
review details the delineation of updated findings and challenges associated with 0D, 1D,
Polymers 2023, 15, 540 8 of 49

factors controlling the performance (hydrophilicity, antifouling, addition of surface charge,

porosity, thermal, mechanical strength, change in surface roughness), and performances
(permeability, selectivity/separation, rejection) will be comprehensively evaluated. This
review details the delineation of updated findings and challenges associated with 0D, 1D,
2D, and 3D nanomaterials-based polymeric nanocomposites with a focus on MF, UF, NF,
RO, and FO, which is beneficial to researchers for prospective materials and techniques. In
addition to this, computational studies leading to better understandings of contaminant or
foulant–membrane interactions, specifically in PA layer to examine antifouling behavior,
are highlighted. Nanostructural forms of biopolymers are discussed to compare with
synthetic inorganic nanomaterials. We will also discuss the environmental impact and
future scope of these nanocomposite membranes. However, it should be noted that the
membrane performance is highly dependent on the test conditions, which are different
for various membrane applications (MF, NF, UF, RO, FO). Our efforts have primarily fo-
cused on a single type of NP-integrated membrane system, but have been extended to
some combinatorial examples to demonstrate remarkable synergy between NPs when
combined. Lastly, this review offers a diverse variety of polymer-nanoparticle thin-film
combinations compared to previously published reviews, as shown in Figure 1. The aim of
this manuscript is to offer a holistic overview of the extensive research conducted that can
aid in the prospective selection of materials, combinations, and technologies primarily for
water and wastewater treatment membrane solutions.

2. Incorporation of NPs in TFNCs/MMMs

2.1. Metal/Metal-Oxide-Based Nanocomposites
The incorporation of metal oxide NPs in polymers leads to the enhancement of var-
ious properties. For instance, enhancement in hydrophilicity is a common trait because
these NPs can absorb hydroxyl groups and form a hydration layer on surface, imparting
hydrophilicity in MMMs [119]. They have inherent antibacterial [108,120–122], antifoul-
ing [123–126], and magnetic properties [127–130]. These traits enhance water flux and
rejection/adsorption capacity properties. Apart from this, low cost, photocatalytic degra-
dation, self-cleaning, and low toxicity are other important features found in metal oxide
NPs [33,119,131–133]. However, metal oxide NPs have issues with uncontrolled colloidal
aggregation at higher concentrations due to organic–inorganic incompatibility [80,134,135],
which affects the specific surface area and reactivity of these NPs and has a negative
impact on the mechanical properties and performance [80] of these systems, resulting in
increased viscosity and pore blocking phenomena [136]. The optimization of the fabri-
cation procedure that allows for a homogeneous distribution of NPs within the polymer
matrix and the targeting of an optimal threshold concentration should be considered to
minimize agglomeration. There has been extensive work carried out proposing optimal
concentrations of incorporated NPs to provide maximum water flux and the highest desali-
nation/adsorption capacity in membranes incorporating metal oxide NPs [80,134,137–140].
Recently, Erdugan et al. fabricated PVC membranes with specially designed hexagonal
platelets of ZnO which exhibited promising UF membrane performance without agglom-
eration issues [106]. Additionally, the risk of leached NPs present in the environment
and potential toxic effects on human health is always an ongoing concern [141–143]. This
incorporation must be tailored in a way that fits the best process tools for environmentally
friendly, high-performance water treatment systems.

2.1.1. Iron-Oxide-Based Nanocomposites

Iron is one of the most abundant and inexpensive elements present on earth and is
widely used for geological and infrastructural purposes [144]. However, nano-dimensional
Fe is highly reactive and unstable, and therefore the oxide forms have been extensively
used [44]. This form of iron is used for incorporation in the polymer matrix as it is low cost,
possesses hydrophilic properties, and has resulted in the enhancement of various prop-
erties discussed further in this section. Upadhyaya et al. evaluated protein permeability
Polymers 2023, 15, 540 9 of 49

performance of hydrophobic and hydrophilic MMMs where hydrophilic and hydrophobic

nanocomposite membranes consisted of casting solutions of polymeric spheres intercon-
nected with quaternized poly(2-dimethylamino)ethyl methacrylate-coated iron oxide NPs
and superparamagnetic NPs consisting of diblock copolymer and stabilizer-coated iron
oxide NPs [127,145]. Application of a magnetic field in these membranes resulted in the
enhancement of permeated flux and a reduction of protein fouling effects, allowing them
to be used as antifouling nanocomposite membranes [146]. Kim et al. synthesized poly-N-
phenylglycine nanofibers grafted onto reduced graphene oxide (GO) sheets intercalated
with Fe3 O4 NPs to form nanocomposites that exhibited a high degradation capacity of Cu(II)
up to 95%. They used density functional theory (DFT) calculations and Perdew–Burke–
Ernzerhof (RPBE) exchange–correlation functional to show that there is stronger binding
due to deprotonated functional groups at higher pH compared to lower pH, resulting in
high sorption efficacy [147]. To reduce agglomeration and enhance interphase compatibility,
surfaces of NPs are modified as well. Nawi et al. fabricated the surface of Fe3 O4 NPs with
polydopamine, followed by functionalization with (3-aminopropyl)triethoxysilane (APTES)
or chlorosulfonic acid, which were impregnated onto hollow PES fibers by the dry/wet
spinning method. These nanocomposite membranes demonstrated an enhancement in
water flux (82.60 → 137.23 L m−2 h−1 bar−1 ) and adsorption capacity (71.92 → 92.16%) of
bovine serum albumin (BSA) when compared to pristine PES fiber [148].

2.1.2. Silver/Zinc-Based Nanocomposites

Foulant build-up can lead to a decrease in membrane water flux with increased run
time, increasing operational costs and shortening membrane life [149,150]. Membrane
fouling can be of various types ranging from crystalline scaling, organic fouling, microbial
fouling, or particulate and colloidal fouling [151,152]. These occur due to the interaction
of the membrane with different sources. Biofouling has detrimental effects on membrane
systems and accounts for 45% of membrane fouling [151]. The incorporation of NPs into
membranes can offer affordable solutions for long-lasting sustainable membranes by in-
creasing the resistance to membrane biofouling. Ag NPs are well known antibacterial agents.
The mechanism of antibacterial activity of Ag stems from the denaturation effect of Ag
ions, which causes the condensed DNA to lose its replication ability. Ag ions interact with
thiol groups present in amino acids, resulting in the inactivation of bacterial proteins [153].
Ag ions have an affinity for sulfhydryl groups exposed on bacteria or viruses, disrupting
the H2 energy transfer system in microorganisms due to the sulfur and Ag bond [154].
Khare et al. added PEG-soaked Ag grown activated carbon microfibers and nanofibers
(Ag-ACFs/CNFs) in situ during emulsion polymerization of PVA, which was casted into a
film followed by the creation of laser ablation microchannels to expose Ag-ACFs/CNFs
dispersed within the polymer matrix. This metal–carbon–polymer-nanocomposite-based
contractor inhibited the growth of gram-negative Escherichia coli (E. coli K-12) and gram-
positive Staphylococcus aureus (S. aureus RN4220) bacterial strains instantaneously under
flow conditions due to the antibacterial property imparted from Ag NPs [155]. Besides
acting as a scaffolding support to Ag NPs, CNFs enhanced the tensile strength and thermal
stability of the film. There are also reports on the antibacterial property of ZnO in the litera-
ture. From previous works, it is well known that the antibacterial activity of ZnO is related
to the generation of H2 O2 on the surface [156,157]. Jo et al. modified PES membranes with
PVP-grafted and poly(1-vinylpyrrolidone-co-acrylonitrile) (P(VP-AN))-grafted ZnO NPs
by the NIPS process. PVP and P(VP-AN) imparted hydrophilicity while ZnO imparted
antibacterial properties. Antibacterial activity was measured in accordance with the JIS
Z-2801 standard and 0.5 wt.% loaded ZnO-modified membranes showed an enhanced
antibacterial activity (0.2 → 6.1) toward E. coli (ATCC 8739) and S. aureus (ATCC 6538P)
when compared to pristine membranes. These PES/polymer-grafted ZnO membranes
demonstrated an increase in water flux and hydrophilicity, but a slight decrease in PEG
rejection with an increase in filler content (>4 wt.%); there were improved antifouling
characteristics compared to the PES membrane only, with no ZnO leaching observed in
Polymers 2023, 15, 540 10 of 49

the modified membrane [158]. Mousa et al. electrospun 0.2 wt.% loaded ZnO NPs in a
blend of PSf and cellulose acetate and coated with a 0.1 M NaOH solution to fabricate a
superhydrophilic nanofibrous membrane. This membrane showed a decrease in water
contact angle (WCA) (72.86 → 13.17◦ ), comparable tensile strength, enhanced water flux
(20 → 460 L m−2 h−1 ), strong antibacterial activity against E. coli with a bacterial growth
inhibition zone diameter of 10 ± 0.6 mm, but low flexibility [108]. Hong and He incor-
porated a PVDF membrane with ZnO NPs and the results revealed an improvement in
photocatalytic self-cleaning efficiency (62 → 93%) and water flux (66.6 → 147.2 L m−2 h−1 ),
and a decrease in WCA (63.21◦ ) with an increase in ZnO NPs content, but led to a decrease
in mechanical strength and chemical oxygen demand removal efficiency after loading was
exceeded beyond 0.01 wt.% [159].

2.1.3. Silica-Based Nanocomposites

The incorporation of silica NPs has been a widely used method due to their chemical,
structural, and thermal stability, facile suspension in aqueous solution, and environmen-
tally benign property [160–162]. For instance, when silica NPs were incorporated in PVDF
membranes, the nanocomposite membranes exhibited higher thermal stability, hydrophilic-
ity, and improved levels of selectivity due to the presence of silica NPs [163]. Additionally,
mesoporous silica are porous nanostructures incorporated to introduce a uniform pore
size distribution [164]. Silica NPs have been incorporated within the polymer matrix or an-
chored on the surfaces of electrospun polymeric fibrous membranes. Pi et al. impregnated
silica NPs on electrospun poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) to
form superhydrophilic multistructured nanofibrous membranes for the removal of Cu(II)
ion, which resulted in an adsorption capacity of 21.9 mg g−1 [165]. A Freundlich adsorption
isotherm and a pseudo-first-order kinetic model was best fit for the experimental data.
Teng et al. electrospun PVP combined with SiO2 to form mesoporous fiber membranes
with thioether group functionalization for selective adsorption of Hg(II). These membranes
demonstrated an adsorption capacity of 852 mg g−1 with an 18% molar concentration of
organosilane precursor [166]. Keshtkar et al. obtained nanofibrous membranes by elec-
trospinning a sol–gel of dispersed SiO2 NPs (7–25 nm particle size), PVP, APTES, and
tetraethylorthosilicate, and demonstrated removal of Cd(II), Pb(II), and Ni(II) with an
adsorption capacity of 157.4, 158.3, and 63.0 mg g−1 , respectively. These experiments
were conducted with initial concentrations of these heavy metal ions ranging between
30 and 500 mg L−1 at pH 6. The BET surface area of these nanoporous membranes was
65.647 m2 g−1 and the adsorption isotherm best correlated with a Langmuir model. The
activity coefficient of the adsorbate was less than 8 kJ mol−1 , indicating that the adsorption
was a physical process [167]. Istirokhatun et al. demonstrated antifouling activity in the
SiO2 -coated PA-based membrane owing to the hydration property of SiO2 . The fabrication
of this membrane is demonstrated in Figure 4 [123]. A summary of key enhancements in
membrane properties due to the inclusion of different types of SiO2 nanoclusters has been
illustrated in Table 2.

Table 2. A summary of enhancements in properties of SiO2 nanoparticle-based nanocomposite

membranes.

Membrane Type Enhancements Due to Modification Reference

Tubular hollow nanofiber PVC High permeation flux, thermal, and
membrane with dispersed hydrophobic stability, outstanding
[168]
hydrophobic nano-SiO2 for water in lipophilicity and
oil emulsion separation superhydrophobicity
Enhanced hydrophilicity, methylene
MSNs (~500 nm) incorporated in blue (MB) rejection (84.7%), but
[164]
presence of PVP in PSf UF membrane decreased water permeability with
increase of MSNs wt.%
Polymers 2023, 15, 540 11 of 49

Table 2. Cont.

Membrane Type Enhancements Due to Modification Reference

Higher thermal stability,
hydrophilicity, porosity, antifouling,
PES-MSNs nanocomposite and water uptake properties.
[134]
UF membranes Properties deteriorate at highest
(4 wt.%) loading due to
agglomeration
Silica NPs grafted onto PHEMA on
PES membrane
(PES)/SiO2 -g-PHEMA
Higher oil–water flux, flux recovery
carboxyl-modified fluorocarbon
ratio, lower flux decline ratio,
surfactant functionalized PEG [169]
antifouling, and
segment: fPEG-COOH; Grafting
self-cleaning properties
fPEG-COOH onto surface of the
PES/SiO2 -g-PHEMA forming
amphiphilic porous membrane
Composite membrane of Ce-doped
Higher tensile strength,
nanosilica dispersed in PSf prepared
hydrophilicity, and antifouling [170]
by sol–gel process for
property, >98% oil retention rate
oil–water separation
Higher surface hydrophilicity, water
Porous MCM-41 silica NPs and
flux/permeability compared to
nonporous silica incorporated into PA
nonporous structure, enhanced salt [171]
thin-film layer via IP process with PSf
rejections (NaCl (98.1%) and
support at the bottom
Na2 SO4 (98.6%))
High water permeance
(0.46 L m−2 h−1 bar−1 ) and high
percentage removal of contaminants
Incorporation of fumed silica NPs
(reactive red (99.99%), direct yellow
functionalized with APTES into
(99.94%), methyl green (99.80%),
chloromethylated PSf matrix using [80]
rhodamine B (99.79%), crystal violet
vapor induced phase inversion and
(98.69%). Negative impact on
NIPS processes
mechanical and selectivity for 3 and
4 mg g−1 loading due to
agglomeration.
PVC: polyvinyl chloride; MSNs: mesoporous silica; PES: polyether sulfone; PEG: poly(ethylene glycol); PSf:
polysulfone; UF: ultrafiltration; PA: polyamide; PHEMA: poly (2-hydroxyethyl methacrylate); APTES: (3-
aminopropyl)triethoxysilane; IP: interfacial polymerization; PI: phase inversion; NIPS: non-solvent-induced
phase separation; NPs: nanoparticles.

Taking the toxicity of NPs into consideration, Paidi et al. demonstrated the application
of 3D mesoporous silica derived from marine diatom T. lunidiana cultures impregnated in
PSf membranes. These membranes exhibited enhanced hydrophilicity and had uniformly
distributed large pores and low surface roughness as observed by scanning electron mi-
croscopy (SEM) (shown in Figure 5) and atomic force microscopy. Silica frustules extracted
from biomass were cleaned using corrosive nitric acid. In addition to the selection of
biomass-derived products, the processing of these materials should also be considered
in regard to the environmental impact. The highest loaded PSf nanocomposites (0.5%
diatom) demonstrated a water flux of ~807 L m−2 h−1 bar−1 at 20 psi operating pressure
and a removal rate of 98.5% and 94.8% for 500 mg L−1 of BSA and 0.1 M of rhodamine,
respectively [172].
 was 65.647 m g and the adsorption isotherm best correlated with a Langmuir model.
The activity coefficient of the adsorbate was less than 8 kJ mol , indicating that the ad-
sorption was a physical process [167]. Istirokhatun et al. demonstrated antifouling activity
in the SiO2-coated PA-based membrane owing to the hydration property of SiO2. The fab-
Polymers 2023, 15, 540
rication of this membrane is demonstrated in Figure 4 [123]. A summary of key enhance- 12 of 49
ments in membrane properties due to the inclusion of different types of SiO2 nanoclusters
has been illustrated in Table 2.

Polymers 2023, 15, x FOR PEER REVIEW 13 of 50

Figure 4.4.Fabrication
FabricationofofSiO 2−coated polyamide-based membrane for high-capacity rejection and
SiO−
Figure 2 coated polyamide-based membrane for high-capacity rejection and an-
antifouling
tifouling activity.
activity. Adapted
Adapted with
with permission
permission from
from Istirokhatun
Istirokhatun et et
al.al. [123]
[123]. . Copyright
Copyright (2021).
(2021). Else-
Elsevier.
vier.

Table 2. A summary of enhancements in properties of SiO2 nanoparticle-based nanocomposite

membranes.

Membrane Type Enhancements Due to Modification Reference

Tubular hollow nanofiber PVC membrane with dis- High permeation flux, thermal, and hydropho-
persed hydrophobic nano-SiO2 for water in oil emul- bic stability, outstanding lipophilicity and super- [168]
sion separation hydrophobicity
Enhanced hydrophilicity, methylene blue (MB)
MSNs (~500 nm) incorporated in presence of PVP in
rejection (84.7%), but decreased water permea- [164]
PSf UF membrane
bility with increase of MSNs wt.%

Figure 5.5. Scanning

Figure Scanningelectron
electronmicroscopy
microscopy (SEM) revealed
(SEM) that pore
revealed that size
poreis size
directly proportional
is directly to
proportional to
diatom loading. SEM surface porosity images of (a) Polysulfone (PSf) with 0.0% of
diatom loading. SEM surface porosity images of (a) Polysulfone (PSf) with 0.0% of diatom, (b) PSfdiatom, (b) PSf
with 0.1
with 0.1 wt.%
wt.%of ofdiatom,
diatom,(c)(c)PSf
PSfwith
with0.20.2
wt.%
wt.%of of
diatom, (d) (d)
diatom, PSf PSf
withwith
0.5 wt.% diatom
0.5 wt.% (×50,000,
diatom (×50,000, 100
100 nm
nm scale
scale barbar
in in
allall micrographs).Adapted
micrographs). Adapted fromfromPaidi
Paidietetal.al.
[172]. Copyright
[172] . Copyright(2022) MDPI.
(2022) MDPI.

2.1.4. Titania-Based Nanocomposites

In addition to antifouling properties, TiO2 NPs also possess tunable morphologies,
facile surface functionalization/modification, chemical stability, low costs, self-cleaning
properties, and photocatalytic activity for organic contaminants, making them suitable for
Polymers 2023, 15, 540 13 of 49

2.1.4. Titania-Based Nanocomposites

In addition to antifouling properties, TiO2 NPs also possess tunable morphologies, facile
surface functionalization/modification, chemical stability, low costs, self-cleaning properties,
and photocatalytic activity for organic contaminants, making them suitable for membrane tech-
nology [173–178]. It is already known that photocatalytic properties of TiO2 NPs help in the
degradation of water contaminants in the presence of an energy source [179–184]. The mecha-
nism of degradation lies in the absorption of energies higher than the semiconductor band
gap, resulting in the excitation of electrons from the valence band to the conduction band.
This leaves a hole in the valence band that can react with water molecules to generate highly
reactive hydroxyl radicals that can oxidize organic contaminants [132]. Aoudjit et al. immo-
bilized Ag-functionalized TiO2 NPs into the poly(vinylidene fluoride-hexafluoropropylene)
matrix and tested photocatalytic activity against an emerging contaminant, metronidazole,
under solar radiation. The results revealed a maximum degradation efficiency of 100%
with an initial metronidazole concentration of 10 mg L−1 at a pH of 7 under 5 h of solar
radiation [185]. Zhang et al. prepared a PVDF nanocomposite membrane by pre-dispersing
TiO2 NPs via PEG additive, which ensured uniformly spaced surface pores, larger porosity,
high water flux, negative zeta potential, and an increased hydrophilicity of the membrane.
This membrane exhibited a higher interaction energy peak compared to the control mem-
branes, which signified the increasing difficulty with which foulants interact with or attach
onto membrane surfaces when evaluated using extended DLVO theory. This, along with
low flux decline from the filtration experiment, corroborates the enhanced antifouling
performance [186]. Like other metal-based NPs, TiO2 NPs have been extensively used in
MF [187–190], NF [191–195], UF [196–200], and RO [201–203] applications. Yu et al. incorpo-
rated TiO2 NPs in a dope containing 18 wt.% PVDF and 5 wt.% additive PVP to formulate
hollow-fiber UF membranes using the sol–gel method and the blending method. Compared
to a pristine PVDF membrane, the addition of 1 wt.% loaded TiO2 NPs using the sol–gel
method enhanced the hydrophilicity (lowering of WCA, 79.13 → 34.91◦ ), thermal stability,
mechanical strength (1.71 → 2.26 MPa), and water permeation (~110 → 244 L m−2 h−1 ) of
this UF membrane, resulting in improved antifouling properties. The hydrophilicity and
permeability subsequently decreased beyond 1 wt.% loading due to an increase in viscosity
and pore blocking phenomena. The sol–gel method resulted in uniformly dispersed TiO2
particles in the polymer matrix compared to the blending method [198]. Key enhancements,
as well as the loading % at which TiO2 agglomeration occurred, have been highlighted
in Table 3 to consolidate the threshold concentration values used by researchers to obtain
best performance.
Hosseini et al. fabricated UF membranes by incorporating TiO2 NPs and observed
that a 7 wt.% loading of TiO2 NPs resulted in the optimal properties of higher porosity,
higher hydrophilicity, water flux, lower flux decline, mechanical stability, high oil rejection,
and antifouling properties. However, higher loading (10 wt.%) resulted in a non-uniform
dispersion, aggregation, and pore blocking of the membrane, which in turn resulted in a
defective structure and a reduction in mechanical strength. Hosseini et al. tested the stabil-
ity of the matrix and observed a 10 wt.% loading to be leaching from the polymer matrix,
which is possible due to non-covalent binding of NPs onto the membrane surface [196].
This is noteworthy while addressing the concern of NPs leaching into the environment.
Mahdhi et al. used the Lifshitz and Young–Laplace theories’ analysis to show that the
incorporation of threshold volume fraction of TiO2 NPs in PVDF, chitosan (CS), and cel-
lulose acetate led to the conversion of the hydrophobic matrix to hydrophilic in nature,
which resulted in the draining of water inside the nanopores without the need for external
pressure or energy opening new avenues for green and sustainable NF membranes [191].
Polymers 2023, 15, 540 14 of 49

Table 3. A summary of key enhancements in properties of TiO2 nanoparticle-based nanocomposite

membranes.

Enhancement and Agglomeration

Membrane Type Reference
Due to Modification
Enhanced porosity, permeability,
hydrophilicity, water uptake,
PSf UF membrane with PANI-coated
antifouling property with a rejection
TiO2 NPs and PEG as additives [204]
of 68% and 53.78% for Pb2+ and Cd2+ ,
fabrication by PI process
respectively. Agglomeration
@ 1.5 wt.% loading.
Enhanced hydrophilicity and
PSf-based PANI-coated TiO2 antifouling property with a rejection
NPs-coated PA nanocomposite of 81.5% and 96.5% for Reactive Black [125]
hollow fiber membrane 5 and Reactive Orange 16.
Agglomeration @ 1 wt.% loading.
Better porosity, hydrophilicity, and
TiO2 NPs incorporated into PSf
antifouling property. Tiny aggregates [124]
UF membrane
@ 2.0 wt.% loading
Enhanced hydrophilicity, antifouling,
Addition of TiO2 NPs in a PVDF and photo-bactericidal effect against E.
sulfonated PES blend membrane coli, higher FRR (86.2%). NPs loading [197]
fabrication by PI method negative effect on pure water flux.
Agglomeration ≥ 4 wt.%.
Enhanced hydrophilicity, mean pore
size and permeation property, flux
Addition of TiO2 NPs in microporous
(3711 L m−2 h−1 ), mechanical [110]
PES membrane
strength, thermal stability.
Agglomeration @ 4–5 wt.% loading.
Enhanced hydrophilicity, mechanical
strength, chemical stability, and
Electrospun nanofibers from a blend
antifouling property with high
of PVP, PVDF and TiO2 NPs [205]
separation efficiency (98.4%) and FRR
(oil–water separation)
(95.68%) (Schematic shown in
Figure 6)
PSf membrane using TiO2 nanorods Enhanced hydrophilicity, high surface
forming flower-like structures used area, self-cleaning efficiency (68.8%), [111]
as additive antifouling activity
Enhanced water flux, direct red-16
L-cysteine-surface-modified TiO2
(98%) and liquorice (90%) removal,
NPs incorporated in PES membrane [140]
hydrophilicity, antifouling.
by PI process
Agglomeration @ 1 wt.% loading
PANI: polyacrylonitrile; PSf: polysulfone; PEG: poly(ethylene) glycol; PI: Phase inversion; PVP: poly(1-
vinylpyrrolidone); PVDF: polyvinylidene difluoride; UF: ultrafiltration; FRR: flux recovery rate.
 show that the incorporation of threshold volume fraction of TiO2 NPs in PVDF, chitosan
(CS), and cellulose acetate led to the conversion of the hydrophobic matrix to hydrophilic
in nature, which resulted in the draining of water inside the nanopores without the need
Polymers 2023, 15, 540 for external pressure or energy opening new avenues for green and sustainable15NFof 49mem-

branes [191].

Figure 6. 6.
Figure Fabrication
Fabricationofofblend
blendcontaining polyvinylidenedifluoride
containing polyvinylidene difluoride and
and TiOTiO 2 nanoparticles into a
2 nanoparticles into
membrane
a membrane for oil–water separation.
for oil–water Adapted
separation. with
Adapted permission
with from
permission fromDuDuetetal.al.[205] . Copyright
[205]. Copyright (2021)
Elsevier.
(2021) Elsevier.

2.2.2.2.
Carbon-Nanostructure-Based Nanocomposites
Carbon-Nanostructure-Based Nanocomposites
Numerousstudies
Numerous studies on
oncarbon-based
carbon-based nanomaterial
nanomaterial adsorbates have been
adsorbates haveconducted be-
been conducted
cause these materials exhibit high specific surface area, mechanical strength, uniform
because these materials exhibit high specific surface area, mechanical strength, uniform porosity,
thermal thermal
porosity, stability, surface reactivity,
stability, surface and chemical stability
reactivity, to harshstability
and chemical conditionsto[206–210]. The
harsh conditions
performance of carbon nanostructures is superior in terms of high-water flux, high ion
[206-210]. The performance of carbon nanostructures is superior in terms of high-water
rejection, and antifouling properties. However, it is critical to note that carbon nanostruc-
flux, high ion rejection, and antifouling properties. However, it is critical to note that car-
tures have intrinsically poor dispersibility and thus agglomerate, which can be avoided by
bon nanostructures
surface have intrinsically
functionalization. poor dispersibility
Carbon nanostructures have been and thus agglomerate,
specifically which can
used as nanofillers
be to
avoided by surface functionalization. Carbon nanostructures have
enhance the mechanical strength and viscoelasticity of polymer matrices [211–213]. been specifically
used ascarbon
Both nanofillers to enhance
nanostructures andthe mechanical
polymer strength
membranes and viscoelasticity
can adsorb of polymer ma-
or capture contaminants;
trices [211-213].
however, their Both carbonwill
mechanism nanostructures and polymer
be different based membranes
on the structure, can adsorb
morphology, or cap-
stack-
ing arrangement, and presence of surface functional groups. Additionally,
ture contaminants; however, their mechanism will be different based on the structure, this section
will providestacking
morphology, a comprehensive summary
arrangement, of computational
and presence studies
of surface used to
functional understand
groups. Addition-
foulant–membrane interactions and antifouling phenomena in PA membranes.
ally, this section will provide a comprehensive summary of computational studies used
to 2.2.1.
understand foulant–membrane
Carbon-Nanotube-Based interactions and antifouling phenomena in PA mem-
Nanocomposites
branes.This class of materials has attracted widespread interest in the scientific community
for a wide range of applications due to their unique properties. The inner diameter of CNTs
2.2.1.
canCarbon-Nanotube-Based
be adjusted within a narrowNanocomposites
range to ensure high-efficiency performance of CNT-based
membranes [214]. Compared to NF and RO membranes, CNT-based membranes are more
resistant to biofouling, thus reducing operating costs [214]. Incorporation of CNTs in the
 This class of materials has attracted widespread interest in the scientific community
for a wide range of applications due to their unique properties. The inner diameter of
CNTs can be adjusted within a narrow range to ensure high-efficiency performance of
CNT-based membranes [214]. Compared to NF and RO membranes, CNT-based mem-
branes are more resistant to biofouling, thus reducing operating costs [214]. Incorporation
Polymers 2023, 15, 540 16 of 49
of CNTs in the polymer matrices leads to better thermal, mechanical, electrical, and rheo-
logical properties, even at low concentrations [213,215,216]. However, CNTs usually ag-
gregate together because of van der Waals interactions, thus the efficient fabrication of
polymer
these matrices
matrices leads toin
is critical better
orderthermal, mechanical,
to optimize electrical, andofrheological
the performance properties,
these nanocomposites
[217]. Shawky et al. synthesized nanocomposite membranes by grafting a PAtogether
even at low concentrations [213,215,216]. However, CNTs usually aggregate substrate
because of van der Waals interactions, thus the efficient fabrication of these matrices is
with multiwalled carbon nanotubes (MWCNTs). It was found that a loading of 15 mg g
critical in order to optimize the performance of these nanocomposites [217]. Shawky et al.
of MWCNT resulted in an increase in salt rejection (24 → 76%) and mechanical properties
synthesized nanocomposite membranes by grafting a PA substrate with multiwalled carbon
(34.3 Mpa) with only a small decrease in water flux (32 → 28−1L m h ) [218]. Dumee et
nanotubes (MWCNTs). It was found that a loading of 15 mg g of MWCNT resulted in
al.anfabricated
increase in a dense layer of(24
salt rejection PA→on76%) a support substrate of
and mechanical a hydroxyl-functionalized
properties (34.3 Mpa) with only CNT
mesh,
a small which
decreaseresulted
in waterin higher
flux (32 porosity
→ 28 L (>90%),
m−2 h−1low WCA
) [218]. Dumee(<20°), and
et al. high water
fabricated uptake
a dense
capacity (17 wt.%) compared to PSf membranes paving the
layer of PA on a support substrate of a hydroxyl-functionalized CNT mesh, which resulted way for FO and RO applica-
tions [219].porosity (>90%), low WCA (<20◦ ), and high water uptake capacity (17 wt.%)
in higher
Lee et to
compared al.PSf
prepared
membranes a microporous
paving the membrane
way for FO by andincorporating
RO applications 0.5[219].
wt.% CNT in PSf
support Leematrix and demonstrated
et al. prepared a microporous an increase
membrane in water flux (268 →
by incorporating 0.5342
wt.%Lm CNT h inbar
PSf ),
−2 −1 −1
surface porosity (1.4 → 3.8%), and salt rejection (97.4 → 97.7%) while maintaining),the
support matrix and demonstrated an increase in water flux (268 → 342 L m h bar
surface
WCA (66.2 → 66.6°).
porosity → 3.8%),
(1.4 This paved and thesalt
wayrejection (97.4 → optimized
for designing 97.7%) while maintaining
supports for FO theand
WCA (66.2 → 66.6osmosis ◦ ). This paved the way for designing optimized supports for FO
pressure-retarded [220]. Using π- π stacking and hydrophobic interactions,
and pressure-retarded
Zhang et al. designed an osmosis [220].
ultrathin filmUsing µm)stacking
(1.5 π-π with anand hydrophobic
entangled meshinteractions,
of CNTs uni-
Zhang et al. designed an ultrathin film (1.5 µm)
formly coated with hyperbranched anthracene ending poly(ether) moietieswith an entangled mesh of CNTs(schematic
uniformly is
coated with hyperbranched anthracene ending poly(ether) moieties (schematic is shown in
shown in Figure 7) [221]. These membranes displayed selective adsorption towards dyes,
Figure 7) [221]. These membranes displayed selective adsorption towards dyes, sep-
separation efficiency of up to 100% for molecules with similar backbones and the same
aration efficiency of up to 100% for molecules with similar backbones and the same
charge states, and the ability to be regenerated without compromising efficiency. For dyes
charge states, and the ability to be regenerated without compromising efficiency. For
such
dyesas erythrosine
such as erythrosineB andB Evans blue,blue,
and Evans adsorption
adsorption capacities
capacities went
wentupuptoto300300µmol
µmolgg−1 for
an initial concentration of 300 µmol L in−61 mL phosphate-buffered aqueous media at pH
for an initial concentration of 300 µmol L in 6 mL phosphate-buffered aqueous media
7.2, proving
at pH these nanocomposites
7.2, proving these nanocomposites to be topromising
be promising nanoadsorbents
nanoadsorbents for wastewater
for wastewater treat-
ment [221].[221].
treatment Wu etWu al.etfabricated an electrospun
al. fabricated an electrospun porous
poroussupport
support layer
layerofofCS/PVP/PVA
CS/PVP/PVAand
single-walled
and single-walled CNTsCNTs (SWCNTs)(SWCNTs) werewereincorporated
incorporated by the
by electrospraying
the electrospraying technique
technique along
with
along CSwithandCS PVP.andOptimized
PVP. Optimized UF thin-film membranes
UF thin-film membranesexhibited a water
exhibited flux of
a water 1533.26
flux of
−2 −1
L m h , which is comparable to commercial PVDF UF membranes. These membranes
1533.26 L m h , which is comparable to commercial PVDF UF membranes. These mem-
branes
also also achieved
achieved excellent excellent dye rejection
dye rejection (malachite
(malachite greengreen
(MG), (MG), 87.20%;
87.20%; MB, MB, 76.33%;
76.33%; CV,
CV, 63.39%) and heavy 2+ , 95.68%; 2+ , 93.86%; Cd2+ ,%; Pb2+ ,
63.39%) and heavy metalmetal
removalremoval
(Cu2+(Cu
, 95.68%; Ni2+, Ni
93.86%; Cd2+,88.52 88.52%;
Pb2+, 80.41%),
in80.41%),
addition intoaddition
havingtoenhanced
having enhanced
antifouling antifouling
properties properties
[217]. [217].

Figure
Figure7.7. Schematic
Schematicof of the
the fabrication of anthracene-ending
fabrication of anthracene-endinghyperbranched
hyperbranchedpoly(ether
poly(ether amine)-
amine)-
coated carbon nanotube thin films formed by vacuum filtration. Adapted with permission
coated carbon nanotube thin films formed by vacuum filtration. Adapted with permission from from
Zhang al.[221]
Zhangetetal. [221].. Copyright (2016)American
Copyright (2016) AmericanChemical
Chemical Society.
Society.
Polymers 2023, 15, 540 17 of 49

2.2.2. Graphene/Graphene Oxide (GO)/Reduced Graphene Oxide

(rGO)-Based Nanocomposites
Due to the hydrophobicity and mono-atomic thickness, graphene has been extensively
researched for membrane separations. Water permeation is extremely restricted in graphene
due to the blocking of passage by the delocalized electron clouds due to π-π conjugation
in the aromatic rings in graphene [222]. However, the adjacent interlayer distance can
be effectively enlarged via intercalation, such as oxidation and subsequent exfoliation,
or defects can be created in the form of pores to enhance membrane permeability while
maintaining salt rejection [223,224]. GO contains several oxygen-rich functional groups
(carboxylic acid, hydroxyl and epoxide groups), making this lamellar 2D structure hy-
drophilic, easily compliable to surface modifications, exhibit better permeability, and have
good dispersibility in a variety of solvents [222,225] Due to this oxidation, GO becomes
insulative, having poor thermal conductivity compared to graphene. Hydrophobicity,
electrical, and thermal conductivity is partially restored by reducing GO as rGO [226].
Each of these forms of graphene is unique and has been extensively investigated for
water and wastewater treatment. Zhang et al. prepared a nanofibrous membrane by per-
forming an imidization reaction on electrospun poly(amide) acid and directly depositing
rGO on the polyimide membrane by dip coating along with solvothermal reduction of
GO. This membrane achieved a 99.19% oil–water separation efficiency, water flux up to
2040.04 L m2 h−1 , and retained its mechanical integrity under harsh conditions making
it an attractive candidate for wastewater treatment [227]. Najafabadi et al. obtained a
nanofibrous membrane by electrospinning CS along with GO. SEM analysis of GO loaded
up to 0.7% found a decreased diameter of the fibers because of the electrical effect GO
had on the precursor gel used for electrospinning. Analysis of the adsorption kinetics was
consistent with external as well as internal diffusion during the sorption process, resulting
in a heavy metal ion adsorption capacity of 423.8, 461.3, and 310.4 mg g−1 for Pb2+ , Cu2+ ,
and Cr6+ , respectively at 45 ◦ C with an equilibrium time of 30 min [228,229]. Kim et al.
described the creation of a FO composite membrane by entwining GO sheets with a cross
linked poly(Nisopropylacrylamide-co-N,N’-methylene-bisacrylamide) network on a highly
porous nylon substrate. This membrane was less than 40 nm and demonstrated a water
flux of 25.8 L m−2 h−1 and a salt rejection of 99.9%. The membrane had excellent chlo-
rine resistance along with structural stability and the potential to be utilized for FO [230].
Wang et al. hot-pressed rGO on an electrospun PAN membrane to obtain a NF desalina-
tion membrane. It exhibited a higher water flux of (8.41 → 15.0 L m−2 h−1 ) compared to
the pristine PAN membranes measured at 10 bars. Moreover, 81% of the initial flux was
regained after regeneration. Due to the size exclusion effect, separation rejections of 90.0%
and 23.8% were achieved for MgSO4 and NaCl, respectively, where the rGO nanochannels
were considered to be narrower than the hydrated ion size of SO4 2− , but wider than the
Cl− hydrated ion size [231]. Ganesh et al. incorporated GO into PSf membranes using the
wet PI method, resulting in an introduction of macrovoids (shown in Figure 8), enhanced
hydrophilicity, water flux, and Na2 SO4 rejection (>40 → 72%) at 4 bar pressure using
2000 ppm loading [232].
Table 4 lists the benefits of impregnating GO in polymer substrates while categorizing
different filtration studies to help rationalize the choice of MF, UF, NF, or RO so as to
maximize either selectivity or permeability. Typically, the water flux decreases from MF
towards RO as the pore size decreases. These membranes are capable of a wide variety
of applications ranging from filtration, separation, adsorption, rejection, antifouling, and
self-cleaning, among others, as cited with specific examples below [233].
Polymers 2023, 15, 540 18 of 49

Table 4. A summary of membrane types, applications, and enhancements in properties of nanocomposites due to incorporation of GO.

Membrane Application Results (Compared to TFCs) References

Enhanced water flux: 1024 L m−2 h−1 ; Acetaminophen rejection: 72%; Triclosan rejection: 81%;
rGO/PVDF MF (1 bar) [234]
Enhanced antifouling
Water flux: 487.8 L m−2 h−1 ; BSA rejection: 92.5%; Enhanced photodegradation efficiency;
TiO2 /GO/PVDF UF (1 bar) [235]
Enhanced antifouling; Self-cleaning
TiO2 @GO/PES UF (1 bar) Water flux: 109.8 L m−2 h−1 ; BSA rejection: 99.1%; MB photodegradation rate: 95.1%; FFR: 86.1% [236]
Water flux: 491 L m−2 h−1 ; Flux loss: 21%; Improved hydrophilicity (86.1 → 62.5◦ ); mechanical strength
Ag@GO/PVDF UF [237]
(1.94 → 2.13 MPa); Enhanced antifouling due to GO
Improved Water flux (0 → 0.15 wt.%): 200 → 440 L m−2 h−1 ; BSA rejection: 95.08%; Flux recovery: 83.07%;
GO-ND/PVC UF (2 bar) [238]
Enhanced hydrophilic, antifouling, and mechanical strength
Enhanced water flux (0 → 0.1% wt./v GO): 112 → 454 L m−2 h−1 ; BSA rejection: 38.6 → 78.3%; Allura red:
GO/PANI/PVDF NF (1 bar) ~80 → 98%; Methyl orange: ~80 → 95%; Enhanced hyrophobicity; degradation temperature: 398 → 470 ◦ C; [239]
Improved Tensile strength: 32 → 90 MPa, Enhanced antifouling
Enhanced water flux (0 → 0.07% wt./v GO): 110.4 L m−2 h−1 ; New Coccine (dye) rejection: 95.1%; NaCl rejection:
COOH-GO/PA NF (10 bar) [240]
25%; Improved hydrophilicity and surface charge density
Enhanced flux: 325.65 L m−2 h−1 ; Methyl blue rejection: ≥99%; Methylene blue rejection: ~99%; Rhodamine B
GO/PPS NF (0.3 bar) [241]
(RhB) rejection: >99%
Enhanced water flux (0 → 50 mg L−1 rGO-NH2 ): 30.44 → 38.57 L m−2 h−1 ; Salt rejection: NaCl: 26.9%, Na2 SO4 :
rGO-NH2 /PA NF (2 bar) [242]
98.5%, MgSO4 : 98.1%, CaCl2 : 96.1%; Improved antifouling properties
Enhanced water flux (GO:Zeolite: 0.07): 15.6→ 34.5 L m−2 h−1 ; Enhanced salt rejection: 82.8 → 96.86%; Higher
Zeolite/GO/PVDF RO (55 bar) [243]
porosity; Improved hydrophilicity
Enhanced water flux (0 → 0.5 wt.% GO): 27.2 → 35.6 L m−2 h−1 ; NaCl rejection: 98.8 → 99.2%; Higher porosity:
GO/PSf RO (55 bar) 63 → 71.1%; Surface free energy: −91.63 → −108.68 mJ m−2 (higher wettability); Enhanced tensile strength: [244]
17.2 → 23.6 MPa
GO: graphene oxide; rGO/PVDF: Injection of rGO dispersion into PVDF membrane; TiO2 /GO/PVDF: Blending of PVDF with TiO2 and GO; TiO2 @GO/PES: layer-by-layer self-assembly
of TiO2 -loaded GO as few layers on PES membrane; Ag@GO/PVDF: Blending of PVDF with Ag-loaded GO; GO-ND/PVC: Incorporation of GO grafted with nanodiamond-COOH
(GO-ND) into PVC membrane via IP method; GO/PANI/PVDF: Incorporation of GO and PANI in PVDF (PI); COOH-GO/PA: Incorporation of Carboxyl functionalized GO in polyamide
(PA) membrane impregnated on PSf substrate via IP; GO/PPS: Nanographene GO stacked on the surface and pore channels of poly(p-phenylene sulfide) membrane by crosslinking
through Ca2+ , Cu2+ , and Mg2+ (solution casting); Embedding amino rGO (rGO-NH2 ) into PA layer on the inner PES hollow membrane (IP process): rGO-NH2 /PA; zeolite/GO/PVDF:
Incorporation of zeolite and GO in PVDF membrane (solvothermal method); GO/PSf: Thin film of PA on Incorporation of GO in PSf (PI method).
Polymers 2023, 15, x FOR PEER REVIEW 19 of 50

Polymers 2023, 15, 540 19 of 49

Figure 8. Cross sectional SEM illustration of (a) pristine PSf, (b) 1000 ppm GO loaded PSf, (c) 2000 ppm
Figure 8. Cross sectional SEM illustration of (a) pristine PSf, (b) 1000 ppm GO loaded PSf, (c) 2000
GO loaded PSf. Adapted with permission from Ganesh et al. [232]. Copyright (2013) Elsevier.
ppm GO loaded PSf. Adapted with permission from Ganesh et al. [232]. Copyright (2013) Elsevier
2.2.3. Computational Studies
2.2.3.MD
Computational Studies
and DFT calculations have been extensively used in water purification and treat-
mentMD and [245–248].
systems DFT calculations have
Simulation been extensively
studies of nanostructuredused in water purification
carbon-based and treat-
thin films
have gained
ment systems increased effort Simulation
[245-248]. by researchers, offering
studies ofnew possibilities and
nanostructured understandings
carbon-based thin films
of the fundamental structural and functional properties of these films.
have gained increased effort by researchers, offering new possibilities and understand- Despite modest
success,
ings the directional
of the fundamental alignment of incorporated
structural and functional CNTsproperties
as nanofillers withinfilms.
of these the polymer
Despite mod-
matrix remains a matter of significant effort. Successfully aligned CNT morphology can
est success, the directional alignment of incorporated CNTs as nanofillers within the pol-
yield maximum theoretical values of salt rejection and water flux. The focus of subsequent
ymer matrix remains a matter of significant effort. Successfully aligned CNT morphology
research has addressed this issue using computational studies. Briefly, Yang et al. annealed
can yield aligned
vertically maximum (VA)theoretical
CNT arraysvaluesat 1500of◦ C,
saltetched
rejection andthe
to open water
CNTs flux.
andThe focus of subse-
embedded
quent research has addressed this issue using computational
within a spin-coated thin layer of polydimethylsiloxane (PDMS) to form a VA open ended studies. Briefly, Yang et al
annealed verticallyThe
hybrid membrane. aligned (VA)
transport CNT arrays
mechanism at 1500
of various °C, etched
classes to open
of molecules (C6the CNTs and
H5 OH,
CO2 , and N2within
embedded ) was evaluated usingthin
a spin-coated DFTlayer
calculations. It was found that the
of polydimethylsiloxane adsorption
(PDMS) to form a VA
energyended
open of phenol on the
hybrid PDMS chain,
membrane. The thetransport
external wall, and the internal
mechanism wall classes
of various of CNT of were
molecules
−1
− 81.0, − 69.5, and − 208.6 kJ mol , respectively, using DFT calculations.
(C6H5OH, CO2, and N2) was evaluated using DFT calculations. It was found that the ad- From experi-
mental results, they found that the single gas permeability of CO and N2 and binary gas
sorption energy of phenol on the PDMS chain, the external2 wall, and the internal wall of
(CO2 /N2 ) separation had superior performances compared to unannealed, close-ended,
CNT were −81.0, −69.5, and −208.6 kJ mol , respectively, using
and unaligned control membranes [249]. Bisignano et al. created an ab initio methodology
DFT calculations. From
experimental results, they
to study the high-capacity found that
rejection of thethe single
small gas permeability
molecular of COcontaminant
weight emerging 2 and N2 and binary

gas (CO
racfluoxetine, glucose, and other small molecules (ethanol, glucose, water) without com- close-
2 /N 2) separation had superior performances compared to unannealed,
ended,
promising andtheunaligned
membranecontrol membranes
flux. This was done by[249]. Bisignano
simulating et al. created
VA MWCNT an ab initio meth-
arrays embedded
odology
within to study
polyester orthe
CS high-capacity
films to form a rejection
nanocompositeof the membrane.
small molecular weight
This novel emerging con-
algorithm
taminant racfluoxetine, glucose, and other small molecules (ethanol, glucose,ofwater)
included a study of functionalized MWCNT edge atoms at their open ends. The ends the with-
tubes were functionalized with polymers with intrinsic
out compromising the membrane flux. This was done by simulating VA MWCNTmicroporosity PIM-1 monomers. It arrays
was observed that the rejection of molecules was in accordance with a size exclusion mech-
embedded within polyester or CS films to form a nanocomposite membrane. This novel
anism with the highest rejection of racfluoxetine achieved using MWCNTs with 4.44 nm
algorithm included a study of functionalized MWCNT edge atoms at their open ends. The
internal diameters. Aligning the MWCNTs can produce a flux that is three times higher
ends of the
than the tubes were functionalized
unfunctionalized membrane. MWCNT with polymers
with 4.44 nm with intrinsic
diameter microporosity
provided the best PIM-1
monomers.
tradeoff between It was observed
water that the
permeability, rejection
effective width of for
molecules
maximum was in accordanceand
functionalization, with a size
exclusion
density of VA mechanism
tubes [250].with the highest rejection of racfluoxetine achieved using MWCNTs
with 4.44 nm internal diameters. Aligning the MWCNTs can produce a flux that is three
times higher than the unfunctionalized membrane. MWCNT with 4.44 nm diameter pro-
vided the best tradeoff between water permeability, effective width for maximum func-
tionalization, and density of VA tubes [250].
Polymers 2023, 15, 540 20 of 49

In a study by Kim et al., a nanocomposite membrane was synthesized using inter-

calation of rGO functionalized with deprotonated poly-N-phenylglycine and Fe3 O4 NPs
that exhibited 95% degradation capacity of Cu(II). DFT calculations with RPBE exchange–
correlation functionals were used to predict sorption affinity for Cu(II) at low and high pH.
They found that there is stronger binding at high pH compared to low pH due to deproto-
nated functional groups. The adsorption process is best characterized as chemisorption at
high pH but physisorption at low pH [147]. Khajouei et al. fabricated an antifouling UF
membrane by incorporating GO NPs in PSf polymer matrix and used OPEN-MX cluster
computing to evaluate the optimal loading percentage for GO deposition within a range
(0.25, 0.5, 0.75, and 1 wt.%). They found that a loading of 0.75 wt.% was the most optimally
stable state and, experimentally, this loading resulted in the optimal tradeoff between
water flux and nitride rejection. Khajouei et al. deduced that for GO loading higher than
the optimal concentration, the performance dropped due to the uncertain position of GO
functional groups on the membrane surface. Wang et al. used a DFT simulation to under-
stand the mechanism of interaction of pharmaceutical contaminants, triclosan (TCS), and
acetaminophen (AAP) with rGO using Vienna ab initio calculations and found that the most
stable adsorption configuration of AAP corresponded to the interaction between acylamino
groups on AAP and hydroxyl groups on rGO with a calculated binding energy of 0.62 eV.
Similarly, the most stable adsorption configuration on TCS corresponded to the interaction
between hydroxyl groups on TCS and hydroxyl groups on rGO with a binding energy of
0.56 eV. This shows that AAP has a higher affinity than TCS to the rGO surface, which is
consistent with filtration experiments of rGO layers on the PVDF membrane (adsorption
capacity of AAP and TCS: 0.023 mmol g−1 and 0.014 mg g−1 , respectively) [234]. A short
summary on the evaluation of foulant and PA membrane interactions using computational
studies have been shown in Table 5.
Another efficient and sustainable method is the grafting of functional polymer bushes
onto or from the surfaces of polymer substrates or nanostructures. This leads to unique
morphologies, thereby exposing functional groups that can readily bind to contaminants.
The covalent grafting of the polymers to the nanostructured scaffold results in reduced
leaching and higher chemical stability for prolonged usage. For example, Ha et al. grew
polystyrene brushes from CNT surfaces by synthesizing vinyl-group-functionalized CNTs
and performing in situ polymerization in the presence of an initiator [251]. Similarly,
poly(acrylic acid) (PAA) brushes were grafted onto the PVDF membrane using a ph-
ysisorbed free radical polymerization technique, and Ag NPs were immobilized on PAA
imparting hydrophilicity, anti-organic fouling, and anti-biofouling properties to the PVDF
membrane [252]. Recently, Ouyang et al. developed an attractive membrane where they
grafted an amphiphilic polymer, PVP, onto the surface of the hydrophobic PP membrane.
This membrane had a water flux of 50,000 L m−2 h−1 bar−1 with an adsorption capacity of
18.5 mg m−2 (42.6 mg g−1 ) for the emerging contaminant bisphenol A (BPA). Regenera-
tion and reusability studies showed that the removal capacity remained above 94% even
after 10 adsorption/desorption cycles of BPA [253]. Sahu et al. fabricated short polymer
brushes of anion exchange resins of vinylbenzyl trimethylammonium chloride and cova-
lently functionalized it onto different carbon nanostructures (SWCNT, fluorographite) in
aqueous media that gave rise to conformally coated pinhole-free mesoporous architecture
and partially exfoliated stacked nanoplatelet-like thin films that delivered a flux capacity of
692 L m−2 h−1 and 1100 L m−2 h−1 , respectively. Functionalized SWCNT demonstrated a
maximum adsorption capacity of 139 mg g−1 for sodium fluorescein and functionalized
fluorographite removed 99% of the emerging contaminant perfluorooctanoic acid to below
100 parts per trillion, which is close to the health advisory limit set by US EPA [74,75,254].
Polymers 2023, 15, 540 21 of 49

Table 5. A summary of findings of computational studies contributing to understanding foulant interactions, effect of ions, and hydration properties of PA
membranes in desalination application.

Membrane Type Computational Method Used Modeling Results Reference

Quenched solid DFT to understand effect
of foulants, moving particle semi-implicit Due to fouling, there was decrease in BET surface area (12.63 → 9.77 m2 g−1 ),
CNT embedded in membrane method to understand implication of average pore size, and pore volume because of saturated mesoporous structure, [255]
foulant (BSA) on velocity and pressure foulant content increasing dead flow section, and membrane pressure
understand foulant (BSA)
Simulation demonstrated higher H2 O diffusion (0.766 × 10−5 →
LAMMPS and OpenMM Ver. 7.5 package
CNT and CNF incorporated 0.923 × 10−5 cm2 s−1 ) after incorporating CNT and CNF compared to pristine
to study hydration and permeation with [256]
in membrane membrane, CNF enhanced water hydration and boron diffusion on the
boron as antiscaling contaminant
membrane, and CNT responsible for increased charge transfer to PA
MWCNT-PA membrane exhibited superior antifouling compared to pristine due
MWCNT incorporated in LAMMPS to study interaction between
to enhanced hydrophilicity, smoother surface, and results in a stiffer PA structure [257]
PA membrane membrane surface and foulant (BSA)
that lowers structural conformity with BSA
MD simulation to study the effect of With increase in ionic strength, no changes were observed for protein-PA
PA and GO membranes presence of ions (Na+ , Cl− ) on membrane while repulsion was observed between protein-GO membrane, PA [258]
BSA–membrane interaction showed attractive interaction with BSA while GO showed a repulsive one
LAMMPS to study effect of ions and Low MW NOM interacts irreversibly with surface cavities of PA, high MW
nanomaterials on membrane fouling alginate either uncoil and spread on the surface or bind to foulant via ionic bridge
CNT incorporated in membrane [259]
during crossflow measurements including due to Ca2+ ions, CNTs induce a stiffer and less rough surface, leading to low
natural organic matter (NOM) or alginate. conformity to foulant interaction
BSA: Bovine serum albumin; PA: polyamide; BET: Brunauer–Emmett–Teller; MWCNT: multiwalled carbon nanotubes; CNF: carbon nanofibers; GO: Graphene oxide; MW: molecular
weight; LAMMPS: Large-scale Atomic/Molecular Massively Parallel Simulator; DFT: Density functional theory.
Polymers 2023, 15, 540 22 of 49

2.3. Zeolite-Based Nanocomposite

As shown in Table 4, membrane performance is an optimization between selectivity
and permeability. Zeolites are a cost effective and green ceramic membrane precursor and
have shown the potential to simultaneously have high rejection/selectivity and high-water
flux [37,260]. Zeolites are three-dimensional porous crystalline structures of aluminosil-
icates with primary building units of alumina or silica tetrahedra that organize to form
secondary building units that are responsible for the development of unique zeolite proper-
ties [261]. Zeolites are classified based on their origin (natural or synthetic), silicon-alumina
ratio, pore size, crystal structure and composition, among other factors [262]. Currently,
there are more than 70 different types of zeolites and more than 200 modified zeolite
frameworks utilized in various engineering applications [260,263,264].
The ability of zeolites to contribute to water treatment applications comes from their
well-defined porous structure with negatively charged surfaces, voids, and flow channels.
These surface charges are balanced by exchangeable ions. Monovalent alkali metal ions and
divalent alkaline earth metal ions within the zeolite structure allow for easy ion exchange
processes [265–267]. Besides metal cations and water molecules in the pores and cavities,
other types of molecules and cationic groups can be accommodated as well. For example,
there is a selectivity order for the exchange of various cations by clinoptilolite zeolite
materials [266]. The silica–alumina ratio in a zeolite is responsible for its chemical stability
and the degree of cationic exchange within the zeolite. Zeolites with low or moderate silica
content exhibit hydrophilicity, electrostatic interaction with polar molecules, and good
adsorption specificity. This gives rise to inter-crystalline defects, which eventually become
a tradeoff for selectivity [268]. Zeolites with higher silica content showcase hydrophobicity
and are better suited for removing emerging contaminants from drinking water [261].
Depending on the width of the flow channels, zeolites can act as molecular sieves, whereas
the width can be tuned by changing the atoms in the framework. Hence, separations in
zeolites can occur via competitive adsorption, ion exchange, molecular sieving, or charge
exclusion mechanisms [269–271].

2.3.1. Naturally Available Zeolites

Clinoptilolites ((K2 , Na2 , Ca)3 Al6 Si30 O72 •21H2 O, monoclinic) are some of the most
abundant and economical zeolites of the heulandite category. They have high crystallinity
and have been extensively used for water treatment [272]. Habib et al. impregnated PVC
membranes with clinoptilolite NPs (0.5 wt.%) and the morphology analyzed under field
emission SEM revealed the presence of larger macrovoids that could facilitate the effective
diffusion of water. The incorporation of clinoptilolite in the nanocomposite membrane
led to higher hydrophilicity owing to the presence of hydroxyl groups and higher water
flux (13.9 → 20.2 L m−2 h−1 ) after 300 min at 0.1 bar pressure, but resulted in a decrease
in mechanical strength. The antifouling performance was improved, with a decrease in
irreversible fouling rate (19.3 → 6%) and an increase of FRR (80.7 → 94%) for a 0.5 wt.%
PVC/clinoptilolite nanocomposite compared to the pristine polymer [273]. Casadellà et al.
prepared MMMs by blending different wt.% of clinoptilolite into PSf and PVP matrix
for selective recovery of NH4+ and K+ . MMMs with 70 wt.% of clinoptilolite particles
showed recovery or desorption capacities of 75% and 60%, respectively, for NH4+ and K+
with H+ ions using ultrapure water at 60 ◦ C [267]. Natural zeolite materials have shown
molecular sieving, high selectivity, and high cation exchange capacity, yet water flux is
often a performance constraint. Moreover, impurities restrict their exchange efficiency.
Many of these limitations can be circumvented using synthetic zeolites [260,274].

2.3.2. Synthetically Available Zeolites

Synthetically produced zeolites have a controlled composition, which can be manufac-
tured at a large scale. Moreover, the structural features of zeolites can be exploited, and the
total molecular charge of the zeolite framework can be modified for specific ion diffusion
and separation technologies. In the following section, a holistic review of mainly syntheti-
 Polymers 2023, 15, x FOR PEER REVIEW 23 of 50

Polymers 2023, 15, 540 23 of 49

the total molecular charge of the zeolite framework can be modified for specific ion diffu-
sion and separation technologies. In the following section, a holistic review of mainly syn-
thetically produced zeolite materials for various water treatment applications are dis-
cally
cussedproduced
in detail.zeolite materials for of
The incorporation various
zeolitewater treatment
into the applications
polymeric are discussed
matrix allows for en- in
detail. The incorporation of zeolite into the polymeric matrix allows for enhanced
hanced chemical and mechanical stability, permeability, selectivity, adsorption, separa- chemical
and mechanical stability, permeability,
tion, and desalination processes [275]. selectivity, adsorption, separation, and desalination
processes [275].
Organic Dyes
Organic Dyes
Zeolites hold remarkable potential in the removal of toxic organic dyes from
Zeolitesdue
wastewater holdtoremarkable
their strong potential in the
electrostatic removal [276-278].
interactions of toxic organic
Song etdyes from wastew-
al. prepared a
ater due to their strong electrostatic interactions [276–278]. Song
robust cellulose nanofibrous UF membrane by embedding Zeolite Imidazole Framework- et al. prepared a robust
cellulose
8 (ZIF-8, nanofibrous
class of metal UForganic
membrane by embedding
frameworks) ZeolitetoImidazole
as an anchor Framework-8 (ZIF-8,
hold 2,2,6,6-tetramethylpi-
class of metal
peridine 1-oxylorganic
radical frameworks) as an anchor
(TEMPO) oxidized to hold
cellulosic 2,2,6,6-tetramethylpiperidine
membrane together using an in situ 1-oxyl
radical (TEMPO)
synthesis (shown oxidized
in Figure cellulosic
9). It was membrane
found out that together
the 21using
wt.% an in situ synthesis
ZIF-8-loaded (shown
nanocom-
in Figure
posite 9). It was
membrane (20found out that the
µm thickness) showed21 wt.% ZIF-8-loaded
optimum nanocomposite
porous structure, with a membrane
smaller
(20
fluxµm
dropthickness)
(29%) and showed optimum
a higher porous
water flux of 84 L m h with
structure, bar a smaller flux drop
as compared to 21(29%)
wt.%and
2 −1
ablend
higher water flux
composite andofpristine h bar−
84 L m−cellulose 1
as compared
nanofibers (CNF)towith
21 wt.%
waterblend
flux of composite
11 and 6and
L m h cellulose
pristine nanofibers
, respectively (CNF)
(after 24 h of with water
filtration (atflux
1–3 of 11 and
bar)). 6L
These m−2 h−1 , respectively
membranes showed
(after
highly24selective
h of filtration
removal(at of1–3 bar)).dyes
cationic These membranes
(Janus showed
Green B, 98.9%; MB,highly
93.8%) selective
compared removal
to
of
negatively charged and neutral dyes due to electrostatic interactions with the negativelyand
cationic dyes (Janus Green B, 98.9%; MB, 93.8%) compared to negatively charged
chargeddyes
neutral nanofibers
due to [279].
electrostatic interactions with the negatively charged nanofibers [279].

Figure 9. A 21 wt.% ZIF–8 loaded 2,2,6,6-tetramethylpiperidine 1-oxyl radical oxidized cellulose

Figure 9. A 21 wt.% ZIF–8 loaded 2,2,6,6-tetramethylpiperidine 1-oxyl radical oxidized cellulose
nanofibers membrane. Adapted with permission from Song et al. [279]. Copyright (2019) Elsevier.
nanofibers membrane. Adapted with permission from Song et al. [279]. Copyright (2019) Elsevier.

Gowriboy et
Gowriboy et al.
al. fabricated
fabricated nanocomposite
nanocomposite membranes
membranes by by blending
blending ZIF-8
ZIF-8 NPs with PSf
NPs with
PSf and CS, which resulted in enhanced crystallinity, hydrophilicity (WCA, 85.7°
and CS, which resulted in enhanced crystallinity, hydrophilicity (WCA, 85.7 → 57.1◦ ), sur-◦ → 57.1°),
surface
face areaarea
(580.94 m2 gm−1g), thermal,
(580.94 ), thermal,
andand mechanical
mechanical stability.
stability. This
This membrane
membrane demon-
demonstrated
strated removal of both cationic and anionic dyes (MB, 94.11%; RhB, 94.01%;
removal of both cationic and anionic dyes (MB, 94.11%; RhB, 94.01%; Acid blue, 86.6% Acid blue, and
86.6% and Congo Red (CR), 85.50%) due to π-π, hydrogen bonding, and electrostatic in-
Congo Red (CR), 85.50%) due to π-π, hydrogen bonding, and electrostatic interactions. The
teractions. The trend of enhancement in porosity and hydrophilicity of these membranes
trend of enhancement in porosity and hydrophilicity of these membranes can be observed
can be observed in Figure 10a [280]. Nanocomposite RO membranes were fabricated by
in Figure 10a [280]. Nanocomposite RO membranes were fabricated by Kim et al. from
Kim et al. from amino groups carrying sulfonated poly(arylene ether sulfonate) and ami-
amino groups carrying sulfonated poly(arylene ether sulfonate) and aminated EMT type
nated EMT type zeolite NPs. These membranes exhibited excellent chlorine resistance as
zeolite NPs. These membranes exhibited excellent chlorine resistance as evidenced by a
evidenced by a negligible reduction in salt rejection (98.8%) and increment in water flux
negligible reduction in salt rejection (98.8%) and increment in water flux (37.8 L m−2 h−1 ) by
(37.8 L m h ) by 12.7% and 2.5 L m h , respectively, after the chlorination test [281].
12.7% and 2.5 L m−2 h−1 , respectively, after the chlorination test [281]. Dai et al. fabricated
Dai et al. fabricated a membrane by electrospinning poly(lactic acid) and ZIF-8 loaded GO
a(ZIF-8@GO)
membraneand by electrospinning poly(lactic along
analyzed for hydrophilicity acid) and
withZIF-8 loaded GO (ZIF-8@GO)
MB photocatalytic degradation.and
analyzed for hydrophilicity along with MB photocatalytic degradation.
The enhanced hydrophilicity was due to the presence of large numbers of hydroxyl The enhanced
and
hydrophilicity was due to the presence of large numbers of hydroxyl and
carboxyl groups on the surface of GO. The mechanism of photocatalytic degradation was carboxyl groups
on
duethe
to surface of GO.
excitation The mechanism
and transfer of photocatalytic
of electrons degradation
from organic ligands was
of ZIF-8 duethat
to GO to excitation
react
and transfer of electrons from organic ligands of ZIF-8 to GO that react with O2 to produce
O2 •− . This radical anion can react with H+ to produce H2 O2 and subsequent side reactions
generate OH• radicals (Schematic shown in Figure 10b). These highly reactive species
cause the photocatalytic degradation of MB (90%), even at low concentrations of ZIF-8@GO
(0.06 mg mL−1 ) [69].
Polymers 2023, 15, 540 24 of 49

Heavy Metals
Heavy metals are a growing concern for environmental pollution due to the rapid
growth of industrialization, agriculture, and urbanization [282]. Over the past decade, con-
sistent efforts have been made to modify the surface of zeolites so that they not only possess
cation exchange properties but also provide high capacity and selective adsorption [283].
ZIF-67 NPs loaded carboxylated GO sheets were impregnated in PSf hollow fibrous mem-
branes, which were used for Cu2+ and Pb2+ removal. These membranes demonstrated a
Langmuir adsorption isotherm with an excellent water flux of 346 L m−2 h−1 and FRR of
95.7%. Adsorption capacities of these membranes for Cu2+ and Pb2+ were 66.4 mg g−1
and 86.4 mg g−1 , respectively, and contaminated water testing resulted in 94.5% and 97.8%
rejections, respectively, without significant loss from regeneration cycles [284]. Qiu et al.
fabricated a TFNC membrane by embedding polydopamine-modified ZIF-8 in a crosslinked
matrix generated by poly(ethyleneimine) (PEI) and 1,3,5-benzenetricarboxylic acid chlo-
ride. This FO membrane exhibited a 95.8% rejection and a 5.95 L m−2 h−1 bar−1 water
permeability for 5.0 mM of MgCl2 under 1.0 bar where this highly selective rejection of
MgCl2 decreased with increased loading of polydopamine-modified ZIF-8. This is mostly
due to the Donnan exclusion effect, resulting in repulsion between divalent cations and
the positively charged surface due to PEI. However, the water flux increased with NP
loading due to the optimal interface voids generating continuous channels, an increase
in pore size, and positive compatibility between ZIF-8 and PA matrix. This membrane
exhibited remarkable FO mode rejection of heavy metal ions (Cu2+ , 99.1%; Ni2+ , 98.3%;
Pb2+ , 97.7%) [285]. Li et al. fabricated a UF membrane by electrospinning ZIF-8 with PAN
solution and demonstrated adsorption efficiencies of 89%, 92%, and 76% for CR, Pb2+ , and
Cu2+ , respectively. Adsorption mechanisms of these contaminants were investigated by
DFT calculations and MD simulations. It was found that all the contaminants easily adsorb
on the ZIF-8 surface via physisorption. In addition to this, some frameworks collapsed due
Polymers 2023, 15, x FOR PEER REVIEW 24 of 50
to release of Zn2+ due to Pb2+ adsorption, meaning ZIF-8 takes up an ion exchange role,
resulting in chemisorption for Pb2+ . MD simulations investigated the dynamic approach of
Cu2+ at ZIF-8 surface and revealed that under 5 ns, all Cu2+ ions migrated into ZIF-8 due
with O2 to produce
to interactions O2•−Cu
between . This radical
2+ and anion
carbon andcan react atoms;
oxygen with Hwithin
+ to produce H2O2 and subse-
20 ns, dynamic equilib-
quent
rium isside reactions
achieved generate
(shown in Figure• radicals
OH 11) [286].(Schematic shown overview
A comprehensive in Figure of
10b). These highly
zeolite–polymer
reactive speciesmembranes
nanocomposite cause the photocatalytic degradation
used for the removal of MB
of heavy (90%),
metals andeven at molecules/ions
other low concentra-
tions of ZIF-8@GO
are shown in Table (0.06
6. mg mL ) [69].

Figure 10.
10. Integration
Integrationofofnew
newmembrane
membrane properties
properties duedue to ZIF–8
to ZIF–8 addition:
addition: (a) Enhanced
(a) Enhanced hydro-
hydrophilic-
philicity in ZIF–8
ity in ZIF–8 modified
modified membrane [280], ©[280]
membrane , © Elsevier,
Elsevier, 2022; (b)2022; (b) mechanism
Possible Possible mechanism
for ZIF–8 for ZIF–8
mediated
mediated photocatalytic
photocatalytic degradationdegradation of methylene
of methylene blue
blue [69], © ACS [69], © ACS
Omega, Omega, 2018.
2018.

Heavy Metals
Heavy metals are a growing concern for environmental pollution due to the rapid
growth of industrialization, agriculture, and urbanization [282]. Over the past decade,
consistent efforts have been made to modify the surface of zeolites so that they not only
Polymers 2023, 15, 540 25 of 49

Table 6. An overview of nanocomposite membranes for the effective removal of especially heavy
metal ions and few inorganic ions and molecules.

Heavy Metal Ion Adsorption Capacity

Nanocomposite
(or Other (mg g−1 ) (or Recovery/ References
Membrane Composition
Molecules/Ions) Removal Rate b (%))
Incorporation of NaX
zeolite NPs into Ni(II), Pb(II) 122.0, 682.0 [265,287]
PSf membrane
Impregnation of zeolite
Cu(II) 38 [288]
and PVP in matrix of PSf
Hybrid membrane made
up of Ca-Activated zeolite, PO34− 70 b [289]
PVP, and PES blend
Fabricating ZIF-8 NPs into As(III), methylene
97.7, 100 b [71]
cellulose UF membranes blue
Mixing of zeolite into
chitosan (CS) and
Cr(VI), Fe(III), Ni(II) 8.84, 6.16, 1.77 [290]
poly(vinyl alcohol) PVA
mixture via electrospinning
Mixture of
Polycaprolactone and clay 29.59, 27.23, 25.36, 32.88
was electrospun Cd(II), Cr(III),
[291]
Cu(II), Pb(II)
Mixture of PVA and clay
14.58, 17.36, 16.46, 16.50
was electrospun
Integrating ZIF-8 NPs into Congo Red,
89, 92, 76 b [286]
PAN UF membrane Pb(II), Cu(II)
Embedding zeolite and
Cu(II) 96.4 b [292]
PVP into PSf matrix
Blending of zeolite into CS
and PVA mixture Cr(VI) 450 [293]
via casting
Incorporating NaX zeolite
into PVA Ni(II), Cd(II) 342.8, 838.7 [294]
via electrospinning
Pd growth on electrospun
mat of zeolite and poly-
Ammonia nitrogen
acrylonitrile-co-methyl 92 b [295]
(NH4 + -N)
acrylate using
electroless plating
Deposition of microfine
Total organic carbon,
powdered zeolite on outer
total nitrogen, ~18, ~20, ~90 b [296]
surface of PVDF
NH4 + -N
fiber membrane
b: Recovery or removal rate in the third column can be identified by values with b superscript.

Desalination
Although TFCs usually consist of a PA layer on top with a porous PSf substrate
to ensure higher permeability than the commercially available cellulose triacetate mem-
branes [297], the loading of zeolite NPs in TFNC membranes has further enhanced the
water permeability and desalination rate [298]. Zeolite materials have been extensively
used to fabricate TFNC from TFC membranes by impregnating NPs in the active rejec-
tion layer of PA or into the PSf substrate to optimize RO and FO specific applications.
Zeolite-loading-based membrane performance is an interplay between the interfacial poly-
 Impregnation of zeolite and PVP in matrix of PSf Cu(II) 38 [288]
Hybrid membrane made up of Ca-Activated zeo-
PO 70 b [289]
lite, PVP, and PES blend
Fabricating ZIF-8 NPs into cellulose UF membranes As(III), methylene blue 97.7, 100 b [71]
Mixing of zeolite
Polymers 2023, 15,into
540 chitosan (CS) and poly(vinyl 26 of 49
Cr(VI), Fe(III), Ni(II) 8.84, 6.16, 1.77 [290]
alcohol) PVA mixture via electrospinning
Mixture of Polycaprolactone and clay was electro-
merization process, surface Cd(II),roughness,
Cr(III), Cu(II), Pb(II)or 29.59,
and voids 27.23, 25.36,
flow channels due to32.88
substrate [291]
and
spun
active layer interactions that endow these membranes with new properties. These modifica-
Mixture of PVA and clay was electrospun 14.58, 17.36, 16.46, 16.50
tions yield enhanced water flux, solute flux, and salt rejection. Cay-Durgun et al. performed
Integrating ZIF-8 NPs into PAN longUFtermmembrane Congo Red,
(3000 h) performance testingPb(II), Cu(II) PSf TFNC
of NPs-loaded 89,membranes
92, 76 b [286]
that exhibited
Embedding zeolite and PVPenhanced into PSf matrix
water permeability, saltCu(II)
rejection, and hydrophilicity96.4 b [292]
(details in Table 7) [299].
Ma et al.
Blending of zeolite into CS and PVA mixture via performed RO and FO tests on a NaY zeolite-loaded TFNC membrane, and for FO
tests, the active-layer-facing-draw Cr(VI)
solution (AL–DS) and 450
active-layer-facing-feed [293]
solution
casting
(AL–FS) orientations were evaluated. In order to minimize internal concentration polariza-
Incorporating NaX zeolite into PVA tion, via
which electrospin-
significantly reduces water permeability, a structural
Ni(II), Cd(II) 342.8,parameter
838.7 denoted [294]
as S
ning (thickness × tortuosity/porosity) and the hydrophilicity of membrane substrate were taken
Pd growth on electrospun mat of zeolite
into and poly-
consideration in FO tests. A lower value of S is+ required for superior water flux perfor-
Ammonia nitrogen (NH4structure,
-
acrylonitrile-co-methyl acrylatemance, usingwhich indicates
electroless lower tortuosity, thinner and higher
92 b porosity [300,301].[295]
B/A is the ratio of solute N)
permeability to water permeability, which is important in the
plating
selectivity process of FO membranes, where a small B/A value means reduced solute back
Deposition of microfine powdered zeolite[301–304].
diffusion on outerTable
Total6 organic
summarizescarbon, total
the enhancement in characteristics and perfor-
~18, ~20, ~90 b [296]
surface of PVDF fiber membrane
mance of FO/RO specific TFNCs nitrogen, NH4 -N
compared
+
to TFCs (or pristine membranes) due to the
b: Recovery
inclusionor
of removal rate in the third column can be identified by values with b superscript.
zeolite particles.

Figure
Figure11.11.
Migration
Migrationbehavior
behavior of Cu2+
of Cu 2+ on
on the ZIF–8framework
the ZIF–8 framework (a–c).
(a–c). Adapted
Adapted withwith permission
permission from from
Li al.
Li et [286]
et al. [286]. Copyright (2022)
. Copyright (2022) Elsevier.
Elsevier.

Table 7. Comparison of zeolite-loaded TFNC membranes with pristine membranes under

Desalination
specific conditions.
Although TFCs usually consist of a PA layer on top with a porous PSf substrate to
Nanocomposite ensure higher permeability than the commercially available cellulose triacetate
Operating/Working
Results References
Membrane Conditions
0.1% (wt./v) loaded 0.4% (wt./v) loaded
Enhanced water Decreased water
RO tests: 500 mg L−1 permeability: (4.0 × 10−12 → permeability
NaCl feed solution 7.1 × 10−12 m Pa−1 s−1 ), (4.13 × 10−12 m Pa−1 s−1 ),
under 2.5 bar reduction of salt rejection improved salt rejection
(95.6 → 77.6%), exacerbation (90.5%), improvement in
Incorporation of NaY in B/A (9.74 → 61.1 kPa) B/A (22.2 kPa)
zeolite NPs into the PA S value (782 ± 160 µm) comparable to Hydration Technology [305]
layer on porous PSf FO tests: Inc. FO membranes
TFNC membrane Both FS and DS at For DS: 1.0 M NaCl, FS: 10 mM NaCl and 0.1% (wt./v) loaded
500 mL min−1 cross TFNC combination: ~50% enhanced water flux in AL-DS
flow rate (30.7 L m−2 h−1 ), ~50% enhanced water flux in AL-FS
FS: 10 mM NaCl or DI (14.6 L m−2 h−1 )
DS: 0.5, 1.0 or 2.0 M For DS: 1.0 M NaCl), FS: DI water and 0.2% (wt./v) loaded
NaCl TFNC combination: ~100% enhanced solute flux in AL-FS,
>100% enhanced solute flux in AL-DS
Polymers 2023, 15, 540 27 of 49

Table 7. Cont.

Nanocomposite Operating/Working
Results References
Membrane Conditions
Incorporation of 0.30 Enhanced water permeance (3.7 → 5.3 µm MPa−1 s−1 ),
wt.% LTA zeolite NPs Long term test (3000 h) enhanced salt rejection: (97.4 → 97.9%), improved contact
[299]
in PA layer on PSf under 200 psi angle before test (62.1 → 95.2◦ ), improved contact angle after
TFNC membrane test (44.0 → 50.8◦ )
Lower S value (0.34 mm) compared to conventional TFNC FO
Optimal compatibility membranes (0.96 mm), enhanced water permeability (128 →
at 0.5 wt.% loading 461 L m−2 h−1 bar−1 ), enhanced hydrophilicity (contact angle,
Incorporation of NaY 53 → 50◦ )
zeolite NPs in the PA For DS: 0.5 M NaCl, FS: DI and 0.5 % (wt./v) loaded TFNC,
FO tests: Both FS and [298]
layer on porous PSf >100% enhanced water flux in AL-DS (43 L m−2 h−1 ), >100%
DS at 500 mL min−1
TFNC membrane enhanced water flux in AL-FS (21 L m−2 h−1 )
cross flow rate
FS: 10 mM NaCl or DI For DS (2.0 M NaCl), FS (DI water), and 0.5 % (wt./v) loaded
DS: 0.5, 1.0 or TFNC, highest FO water flux reported under similar
2.0 M NaCl conditions (86 L m−2 h−1 )
Enhanced surface porosity (80 → 85.4%), better water
permeability (118.2 → 185.3 L m−2 h−1 bar−1 ), lower S value
Optimal compatibility (0.78 → 0.48 mm), enhanced hydrophilicity (contact angle,
at 0.4 wt.% loading 71.45 → 57.24◦ ) (surface of clinoptilolite modified with
hexadecyl trimethyl ammonium bromide to
Incorporation of
enhance hydrophilicity)
surface-modified
clinoptilolite into PSf RO tests: 20 mM NaCl For 0.4 wt.% loading, enhanced water permeability (1.93 →
substrate by phase aqueous solution at 2.74 L m−2 h−1 bar−1 ), exacerbation in B/A value (9.86 → [306]
inversion method and 2.5 bar 13.99 kPa), slightly reduced salt rejection (96.2% → 94.7%)
coating of PA layer
FO performance for 10 mM NaCl as FS and 2 M NaCl as DS
on top
in AL-DS orientation (for 0.4 wt.% loading): ~50 % enhanced
FO tests:
water flux in AL-DS (33.1 L m−2 h−1 ), >50% enhanced water
FS: 10 mM NaCl
flux in AL-FS (~24.1 L m−2 h−1 ), >100% enhanced solute flux
DS: 0.5 or 2.0 M NaCl
in AL-FS (~15 L m−2 h−1 ), ~100% enhanced solute flux in
AL-DS (~20 L m−2 h−1 )
RO: reverse osmosis; FO: forward osmosis; AL-DS: active-layer-facing-draw solution; AL-FS: active-layer-facing-
feed solution.

Overall, the high thermal and chemical stability as well as the tunable porous structure
make the zeolite system ideal for high water flux treatment applications. Moreover, the
ion exchange and molecular sieving properties make zeolites and related frameworks
promising alternatives for molecule/ion removal, recovery, and desalination [274].

2.4. Biopolymer-Based Nanocomposites

Biopolymer nanocomposite technologies have received significant interest in recent
years due to their promising applications as sustainable water purification membranes.
However, research on these materials is mostly limited to MF, UF, or NF applications [307].
Although biobased polymeric membranes have been widely researched, issues related
to structural robustness, high-capacity removal, resistance to external conditions, and
long-term performance are salient features that need to be carefully assessed. Xie et al. re-
constituted aquaporin Z (channel proteins) into self-assembled poly(2-methyl-2-oxazoline)-
block-poly-(dimethysiloxane)-block-poly(2-methyl-2-oxazoline) vesicles and immobilized
the protein onto a porous cellulose acetate membrane to enhance the membrane stability.
For the membranes incorporated with aquaporin Z, the salt rejection rose from ~0% in
the control sample to 61% and 75% for NaCl and MgCl2 , respectively. These membranes
demonstrated a water flux of ~23 L m−2 h−1 bar−1 while maintaining a high mechani-
cal strength, proving to be a promising candidate for NF or FO application [308]. This
section will shed light on some of the developments on biodegradable cellulose-based
Polymers 2023, 15, 540 28 of 49

and chitosan (CS)-based membranes leading towards advanced water and wastewater
treatment applications.

2.4.1. Cellulose-Based Nanocomposites

Cellulose, the world’s most abundant biopolymer, has been extensively studied for
both its multitude of facile modification mechanisms and its incorporation into water and
wastewater treatment systems. The first RO membranes were cellulose acetate based [309].
The primary C-6 and the secondary C-2 and C-3 hydroxyl groups on the D-glucose
monosaccharide units allow a variety of reactive mechanisms to be employed [310–313].
To be used for water purification and treatment, cellulose has been modified using es-
terification [314], etherification [315], halogenation [316], phosphorylation [317], xantha-
tion [318], oxidation [319], sulfonation [320], carboxymethylation [321], hydrolysis [322],
nitro-oxidation [323], and polymer surface functionalization [324,325] methods. These
modifications can help fine tune their affinity towards specific contaminates and/or add
beneficial features [314,324,326–329].
Interest in cellulosic nanomaterials is due in part to their high abundancy, low cost,
biodegradability, sustainability, thermal stability, high flexibility, low density, and mechan-
ical strength [325,330–333]. However, despite their environmental benefits due to their
biodegradability, the long-term performance of these membranes remains a problem as they
are susceptible to bacterial breeding, which needs to be improved. In a study by Xu et al.,
cellulose nanocrystals (CNC)/Ag were embedded into the PA layer of TFNC NF membrane,
and 0.01 wt% CNC/Ag loading resulted in high water permeability (25.4 L m−2 h−1 bar−1 ),
a high NaSO4 rejection rate (99.1%), and remarkable antifouling (FFR: 92.6% for humic acid)
and antibacterial activity (reduction in E. coli viability: 99.4%) [334]. Though CNCs are usu-
ally processed by the acid hydrolysis method [335], a plant-based or green-chemical-based
modification is of prospective research interest. Zhang et al. fabricated a nanocomposite
membrane incorporating Ag-loaded TiO2 NPs, CNF, and CS that was capable of bacterial
eradication (E. coli, 99.97%; B. subtilis, 99.98%; S. aureus, 99.98%), high oil–water emulsion
(~98.5%), and high MB photodegradation (96.25%) [336]. Yang et al. formulated clean water
remediation by forming copolymers of tobramycin and dopamine through mussel mim-
icked polymerization (PDA/TOB) and coated these PDA/TOB NPs on a cellulose acetate
membrane. These highly durable membranes exhibited remarkable photothermal efficiency
and antibacterial properties, which were used for solar mediated steam generation. These
low-cost membranes exhibited an evaporation rate of 1.61 kg m−2 h−1 and evaporation
efficiency of 92.4% under 1 sun irradiation [337]. Chemically or mechanically modified
cellulosic nanomaterials have been reported to have a remarkably high affinity towards
various heavy metals from drinking water. These include Cd(II), Cu(II), Pb(II), Hg(II), Ni(II),
Cr(III) [315], Ag(I), Co(II), As(V), and Zn(II) [338]. For cellulosic materials, the two main
mechanisms involved in the removal of heavy metal ions are ion exchange and chemical
complexation mechanisms [339]. Cellulose materials possess excellent hydrophilicity due
to the presence of -OH groups on their surface, making them perfect additives for TFNC
membranes [340]. Hoang et al. deposited cellulose nanocrystals (CNC) as an interlayer
on PES substrate and a barrier layer was fabricated using the IP method. For a loading of
5.5 mg cm−2 of CNCs, the water flux (23.92 L m−2 h−1 ) was increased by >70% compared
to the pristine TFC membrane and demonstrated exceptional removal efficiency for toxic
heavy metals (CuSO4 , 98%; CuCl2 , 96.5%; PbCl2 , 90.8%) [341]. A selective ion permeation
membrane was prepared by vacuum filtration of a mixed solution of bacterial cellulose
(BC) and GO, where porous BC layers were intercalated between GO sheets that added
to the stability and tensile strength of these membranes. These membranes operated on
the size exclusion principle where large molecules like RhB and MO are rejected and small
(hydrated radii < 1 nm) inorganic ions (Ni2+ , Mn2+ , Cl− , [Fe(CN)6 ]3− ) permeate through it
at a rate inversely proportional to their size (Figure 12) [70].
FOR PEER REVIEW 29 of 50
Polymers 2023, 15, 540 29 of 49

Figure 12. Mechanisms

Figure of
12. free–standing bacterial cellulose
Mechanisms of free–standing bacterialand graphene
cellulose oxide oxide
and graphene membrane
membraneforfor
se-
lective ion permeation. Adapted with permission from Fang et al. [70]. Copyright (2016) Scientific
selective ion permeation. Adapted with permission from Fang et al. [70]. Copyright (2016)
Reports. Scientific Reports.

TEMPO-oxidized cellulose nanofibers (CN) were embedded within stacked GO sheets

TEMPO-oxidized cellulosewas
and the dispersion nanofibers
coated onto(CN)
a PVDFweremembraneembedded withinwith
to obtain MMMs stacked GO
high water
−2 −1 −1
permeability (816 L m h bar ) and efficient removal
sheets and the dispersion was coated onto a PVDF membrane to obtain MMMs with high (82–99%) of neutral, anionic, and
cationic dyes. They performed reactive MD simulation calculations to understand the
water permeability (816 L m h bar ) and efficient removal (82–99%) of neutral, ani-
mechanism of rejection, which revealed that the dyes exhibited adsorption behavior based
onic, and cationicondyes. Theyπ-π
H-bonding, performed reactivebetween
stacking interactions MD simulation
dye molecules calculations
and GO planes, toand
under-
self-
stand the mechanism
assembly of [342].
rejection, which
Ma et al. revealed
incorporated thatMWCNT
CN and the dyes exhibited
in the adsorption
PVA barrier layer of TFNC be-
composed of a PAN scaffold mid-layer and polyethylene
havior based on H-bonding, π-π stacking interactions between dye molecules and GO terephthalate non-woven substrate
for UF applications. Compared to commercial PAN10 UF membranes, they achieved
planes, and self-assembly
10 folds higher[342]. Ma et flux
permeation al. incorporated CN and
by adding nanofillers MWCNT
without in thethePVA
compromising bar-
rejection
rier layer of TFNC composed
ratio of a PAN scaffold mid-layer and polyethylene terephthalate
(~99.5%) [343].
non-woven substrateThefor dispersion of cellulosic nanomaterials
UF applications. Compared in tohydrophobic
commercial polymer
PANmembranes
10 UF mem- is
one of the ongoing challenges associated with these materials. However, it has been
branes, they achieved 10 folds higher permeation flux by adding nanofillers without com-
reported that surface grafting with polymers can potentially be a solution [339]. Nazri
promising the rejection ratio (~99.5%)
et al. incorporated [343]. cellulose (MCC) into hydrophobic PES matrix using
microcrystalline
The dispersion of cellulosic
the NIPS method andnanomaterials
found that 3 wt.%in MCChydrophobic polymer
resulted in improved membranes
water permeabilityis
−2 −1 −1
(51.50 L m h bar ) compared to the pristine
one of the ongoing challenges associated with these materials. However, it has membrane and a 96.14% humic
beenacid re-
rejection. Although the inclusion of MCC results in a better PI rate, leading to elongated
ported that surface grafting with polymers can potentially be a solution [339]. Nazri et al.
and bigger pore sizes benefiting the flux response, it is important to note that 3 wt.% loading
incorporated microcrystalline cellulose
also reduced the tensile strength(MCC)
(6.57 → into hydrophobic
5.71 MPa) compared to thePES matrix
pristine usingdue
membrane the
NIPS method andtofound that 3 wt.%
an aggregation issue inMCC resulted
the casting in improved
solution water have
[340]. Other studies permeability
shown better (51.50
flux
−2 −1 −1 −2 −1 −1
responses, 485 L m h bar [344] and 692 L m
L m h bar ) compared to the pristine membrane and a 96.14% humic acid rejection. h bar [345], when using CNC and
lignin cellulose nanofibrils in the PES membrane in the presence of PVP additive, which
Although the inclusion
adds to theof pore-forming
MCC results in a better
property PI rate,
and reduce leading toofelongated
the aggregation NPs. and bigger
pore sizes benefiting the flux response, it is important to note that 3 wt.% loading also
reduced the tensile strength (6.57 → 5.71 MPa) compared to the pristine membrane due to
an aggregation issue in the casting solution [340]. Other studies have shown better flux
responses, 485 L m h bar [344] and 692 L m h bar [345], when using CNC and
lignin cellulose nanofibrils in the PES membrane in the presence of PVP additive, which
adds to the pore-forming property and reduce the aggregation of NPs.
Polymers 2023, 15, 540 30 of 49

2.4.2. Chitosan-Based Nanocomposites

Much like cellulosic nanomaterials, advantages such as low cost, high abundancy, reac-
tivity, high hydrophilicity, biodegradability, and biocompatibility make CS nanocomposites
a subject of interest in the current fields of water and wastewater treatment [346,347]. CS
has a similar structure to cellulose, with C-2 acetamido groups and amine groups replacing
the C-2 secondary hydroxyl groups. This allows for an abundance of amino and hydroxy
groups, which can chelate with positively charged metal ions, cationic molecules, and
negatively charged metal oxyacid ions via electrostatic interactions; therefore, it is widely
used in heavy metal removal [217,348–350]. CS has been employed in various forms for
water treatment, such as NPs [351], fibers [352], coatings [353], flakes [354], nanorods [355],
membranes [356], and hydrogels [357], among others. However, pristine CS possesses
low thermo-mechanical properties, low porosity, and poor stability, and therefore requires
reinforcement to enhance the membrane’s mechanical strength [358,359]. Hydroxyapatite
was introduced in the CS solution to form electrospun nanocomposite membranes because
pristine CS renders low flexibility, high viscosity, and poor mechanical properties, making it
difficult to handle. These membranes delivered an exceptional adsorption capacity of 296.7,
213.8, and 180.2 mg g−1 for heavy metal ions Pb2+ , Co2+ , and Ni2+ , respectively, within
30 min equilibrium time at 45 ◦ C. The sorption followed pseudo second order kinetics and
a Langmuir adsorption isotherm [348]. Aliabadi et al. electrospun polyethylene oxide and
CS solution, which formed sorption-selective nanocomposite membranes for heavy metals
in the order: Ni2+ (175.1 mg g−1 ) > Cu2+ (163.7 mg g−1 ) > Cd2+ (143.8 mg g−1 ) > Pb2+
(135.4 mg g−1 ). These nanofibers exhibited an average surface area of 312.2 m2 g−1 using
BET analysis. Regeneration and reusability studies for 5 cycles showed gradual reduction
in capacity due to the loss of active sites during acid regeneration [347]. In another study,
CNCs with functional groups (SO3− and/or COO− ) were incorporated in the CS matrix via
the freeze-drying method and cross-linking was performed using glutaraldehyde vapors.
This membrane was successfully used for the removal of the positively charged dyes (Victo-
ria Blue 2B, 98%; methyl violet 2B, 84%; Rhodamine 6G, 70%) after 24 h and demonstrated
a water flux of 64 L m−2 h−1 . CNC was not only used as a reinforced nanofiller, but also
provided functional sites for high capacity adsorption [360].
CS has been employed to form nanocomposite membranes using solvent casting,
solvent evaporation, and electrospinning techniques to obtain the desired porosities and tar-
geted functionalities for specific adsorption. Gharbani et al. fabricated PVDF/g-C3 N4 /CS
membrane via dissolution casting and demonstrated a removal rate of 72.74% for an ini-
tial concentration of 2 mg L−1 RhB under a pH of 3 and 3% CS loading [361]. Huo et al.
fabricated a sustainable acid-resistant CNF/CS membrane using the solvent casting and
solvent evaporation method and demonstrated anionic MO removal with an adsorption
capacity of 655.23 mg g−1 due to H-bonding, charge interaction, and n-π stacking interac-
tion with no affinity towards cationic dyes (MB and MG). This membrane demonstrated a
slight reduction (98.50 → 89.65%) in MO adsorption in reusability experiments after six
cycles [362]. Wu et al. fabricated an electrospun porous support layer of CS/PVP/PVA, on
which an active layer coating of SWCNT/CS/PVP was performed using the electrospray
method, and was finally crosslinked by glutaraldehyde vapors. Optimized UF thin-film
membranes exhibited a water flux of 1533.26 L m−2 h−1 comparable to a commercial PVDF
UF membrane, a high dye rejection (MG, 87.20%; MB, 76.33%; CV, 63.39%), heavy metal re-
moval (Cu2+ , 95.68%; Ni2+ , 93.86%; Cd2+ , 88.52 %; Pb2+ , 80.41%), and enhanced antifouling
properties [217]. Montaser et al. developed antimicrobial activity in CS by reacting CS with
salicylaldehyde as a crosslinker using Schiff base reaction which resulted in salicylimine-
functionalized CS that formed a metal complex with TiO2 NPs to form the nanocomposite
membrane. These membranes demonstrated full bacterial eradication of S. aureus and
P. aeruginosa at two different concentrations (0.25 × 10−2 and 0.5 × 10−2 g mL−1 ). The
tensile strength and elongation were enhanced due to the integration of TiO2 NPs [363].
Yu et al. fabricated a membrane consisting of modified cellulose acetate, modified CS,
and TiO2 for oil–water separation and Cu2+ adsorption. In order to improve the heavy
Polymers 2023, 15, 540 31 of 49

metal adsorption capacity of these membranes, the amino groups in CS were modified
into N-salicylic groups using the Schiff base. This membrane exhibited 99.4% oil–water
separation efficiency for cyclohexane. At neutral pH, the adsorption capacity for Cu2+
was 220.67 mg g−1 and for a concentration of 1000 mg·g−1 , the adsorption efficiency was
97% [364]. Habiba et al. electrospun a nanofibrous composite of CS/PVA/zeolite that
exhibited a 100% increase in Young’s Modulus because of the incorporation of zeolite and
an adsorption capacity of 153 mg g−1 for MO dye [365].
By 2025, more than 20,000,000 end-of-life RO membranes will be generated globally
per year [307]. Therefore, using biopolymers for RO techniques will alleviate the waste
and its environmental impact. However, fouling of these biobased membranes is one of
the challenging issues while addressing membrane performance. Hegab et al. generated a
layer of chemically functionalized CS with GO by forming amide bonds between carboxylic
groups and amino groups of GO and CS, respectively. This layer was fabricated on a TFC
PA membrane, which was tested against fouling resistance using BSA. This functionalized
membrane exhibited enhanced permeation flux (56.1 → 61.5 L m−2 h−1 ), salt rejection
(88.7 → 95.6%), and FRR (86 → 97%) compared to the pristine PA layer [366].

3. Summary, Impact, and Future Scope

This review summarizes the state-of-the-art as well as comprehensive advances in
the integration and distributions of various NPs, with morphologies that optimize the
performance of nanocomposite membranes used for water treatment applications. Vari-
ous fabrication techniques in terms of loading positions of NPs and types of polymeric-
or NP-based TFNC membranes are summarized in Figure 13. These membranes target
emerging contaminants in the form of toxic molecules or ions in purified drinking wa-
ter and wastewater. For example, several polymer nanocomposite studies have been
conducted using different NPs such as silica NPs [367], nanoscale zero-valent iron [368],
poly(piperazineamide) [369], selective polyamide layer [370], montmorillonite [371], nano-
sized MoS2 [372], GO [373], MWCNT [374], cellulose [324], etc., to achieve the efficient
removal of PFAS, one of the proposed emerging contaminants by the US EPA. In addition
to removing pollutants, the merits of integrating NPs in membrane filtration technolo-
gies includes the addition of structural and chemical properties such as chemical and
thermal stability, antifouling, addition of surface charge, mechanical strength, enhanced
hydrophilicity, porosity, tunable pore size and permeability, among others [215,375,376].
These nanoadsorbents save time and energy during the water and wastewater treatment
processes [375]. Despite their extensive use and high removal capacity, nanomaterials have
underlying issues keeping them from widespread applicability. Past studies have shown
issues of interface incompatibility between the organic polymeric layer and inorganic
NPs [377–380]. This incompatibility leads to the detachment or leaching of nanomaterials
from the membrane surface, which not only affects the efficiency of purification but also
leads to secondary environmental contamination [40,65]. Exposure of nanomaterials into
the environment, including natural water resources, can result in undesired toxicity and
risks that need to be systematically assessed. To minimize leaching, further research is
needed on reliable techniques such as covalent attachment, grafting, or cross-linking to
enhance the binding between NPs and the polymer matrix. A second issue, due to incom-
patibility and high surface reactivity, is agglomeration of NPs. Unoptimized membrane
fabrication or long-term use can challenge membrane performance through the formation
of undesirable voids and cracks [54,381–383].
Polymers 2023,
Polymers 2023, 15,
15, 540
x FOR PEER REVIEW 32
32 of 50
of 49

Figure 13.
Figure 13. Various
Variousapproaches
approaches of of
fabricating polymers
fabricating polymersandand
nanomaterials into membranes
nanomaterials for water
into membranes for
treatment applications: (a) cysteine-grafted cellulose nanofibers impregnated in electrospun poly-
water treatment applications: (a) cysteine-grafted cellulose nanofibers impregnated in electrospun
acrylonitrile scaffold (microfiltration) [384], © Elsevier, 2014; (b) Graphene oxide (GO)-coated chi-
polyacrylonitrile scaffold (microfiltration) [384], © Elsevier, 2014; (b) Graphene oxide (GO)-coated
tosan nanoparticles incorporated into (TFN-M) or at the bottom (TFN-U) of polyamide (PA) layer
chitosan nanoparticles incorporated into (TFN-M) or at the bottom (TFN-U) of polyamide (PA) layer
during interfacial polymerization process (ultrafiltration) [64], © Elsevier, 2021; (c) carboxylated
during interfacial polymerization process (ultrafiltration) [64], © Elsevier, 2021; (c) carboxylated
carbon nanofibers embedded into polysulfone layer via phase inversion process with PA layer on
carbon nanofibers embedded into polysulfone layer via phase inversion process with PA layer on top
top (forward osmosis) [385], © Elsevier, 2020; (d) GO coated on PA layer via layer-by-layer tech-
(forward osmosis) [385], © Elsevier, 2020; (d) GO coated on PA layer via layer-by-layer technique [386],
nique [386], © Elsevier, 2022; (e) Vacuum filtration of bacterial cellulose and GO dispersion [70], ©
© Elsevier,Reports,
Scientific 2022; (e) Vacuum
2016; filtrationbased
(f) Membrane of bacterial cellulosefibers
on electrospun and GO dispersion [70],
of homogenous © of
slurry Scientific
polyvi-
Reports, 2016; (f) Membrane based on electrospun fibers of homogenous slurry
nylidene difluoride and GO mixed with metal organic framework [67], © Elsevier 2022. of polyvinylidene
difluoride and GO mixed with metal organic framework [67], © Elsevier 2022.
The isolation and reusage of these materials for water treatment or other applications
The isolation and reusage of these materials for water treatment or other applica-
could be a possible solution, which supports a circular economy [387-389]. The synthesis
tions could be a possible solution, which supports a circular economy [387–389]. The
and fabrication of adsorption and purification membranes should use green chemicals
synthesis and fabrication of adsorption and purification membranes should use green
and/or solvents to allow a relatively benign approach and reduce the possibility of sec-
chemicals and/or solvents to allow a relatively benign approach and reduce the possibil-
ondary contamination [74,254,390,391]. To alleviate the general environmental contami-
ity of secondary contamination [74,254,390,391]. To alleviate the general environmental
nation problem, the use of nanomaterials with photocatalytic activity can be implemented,
contamination problem, the use of nanomaterials with photocatalytic activity can be imple-
which would
mented, whichallow forallow
would the breakdown of the extracted
for the breakdown contaminants,
of the extracted making the
contaminants, effluent
making the
or secondary waste stream free of contamination [375]. However, high operating
effluent or secondary waste stream free of contamination [375]. However, high operating costs and
reliance
costs andonreliance
UV radiation
on UVmakes this makes
radiation systemthis
inefficient
system[392]. Additionally,
inefficient it is necessary
[392]. Additionally, it
to evaluate the various byproducts of the photocatalyzed degradation, and
is necessary to evaluate the various byproducts of the photocatalyzed degradation, and whether this
process generates
whether this processsecondary,
generatesand possiblyand
secondary, worse, contaminants.
possibly All of the fabrication
worse, contaminants. All of the
techniques employing modifications in PSf membranes are relatively
fabrication techniques employing modifications in PSf membranes are relatively expensive. There-
expensive.
fore, there is a tradeoff between cost efficiency and performance [393]. In order
Therefore, there is a tradeoff between cost efficiency and performance [393]. In order to to ensure
Polymers 2023, 15, 540 33 of 49

ensure cost effectiveness and long-term use, regeneration and reusability are important
factors to be considered for these nanocomposite membranes [43,54,74,75,393].
There has been significant research performed to design and synthesize novel high-
capacity, green, sustainable polymer-based nanocomposite membranes for water and
wastewater treatment. Despite these consistent efforts, several obstacles exist due to lack of
research studies that can be used as a guide for commercial production [40]. Biodegradable
polymeric membranes have been attractive for their ability to harness the hierarchical
structural and mechanical properties of naturally produced biomaterials, leaving a van-
ishingly small human footprint on the environment. Nanomaterials are also designed to
reduce the impact on the environment by providing highly efficient and reusable solu-
tions [394]. For example, nanomaterials have been used in automotive exhaust systems to
promote reactions that reduce pollution and promote cost efficiency [395]. It is important
to harness the positive effects of nanomaterials that can lead to efficient and sustainable
TFNC membrane systems. Computational chemistry methods are useful and convenient
tools in this case to understand small scale complexities of novel membrane structures,
characteristics, and/or performance. This review provides an overview of the extensive
research that has been done in laboratories or at the pilot scale on various combinations
that can help researchers in selecting the required materials and techniques. The future
research scope includes the evaluation of long-term viability with a focus on regeneration
and reusability of nanocomposite membranes with real feed solution testing, environmental
contamination due to membrane processing, cost efficiency, and scaling up raw material
production [40]. To meet the global demand for clean and safe drinking water, these knowl-
edge gaps require further investigative research efforts to improve the understanding of the
commercial-scale production of affordable, efficient, and sustainable water and wastewater
treatment membranes.

Author Contributions: A.S.: conceptualization; investigation; data curation; writing–original draft

preparation; writing–review and editing, acquiring figure permissions. R.D.: writing–original draft
preparation, investigation. C.K.: writing–original draft preparation, investigation. S.S.: writing–
original draft preparation; writing–review and editing, investigation. J.C.P.: writing–review and
editing, investigation, supervision, project administration, fund acquisition. All authors have read
and agreed to the published version of the manuscript.
Funding: This material is based upon work supported by the National Science Foundation under
Grant No. (2141056).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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