Materials Today Chemistry 27 (2023) 101344

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Materials Today Chemistry

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Amine-rich polymers for water purification applications

M.E. Elhalwagy a, b, *, A.S. Elsherbiny a, A.H. Gemeay a
a
Chemistry Department, Faculty of Science, Tanta University, Tanta, 31527, Egypt
b
Ethylene Production Sector, SidiKerir Petrochemicals Company, Alexandria, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Water pollution induced by biological, agricultural, and industrial activities has risen to prominence as a
Received 21 March 2022 scientific issue as it poses a direct threat to life or water scarcity. Thus, it has become critical to design
Received in revised form and develop nanomaterials and understand their properties to combat water pollution. Herein, a survey
16 November 2022
of amine-rich polymers (ARPs) was conducted. They were classified based on the source of their raw
Accepted 2 December 2022
Available online xxx
materials, whether natural or synthetic. The chemical structure and essential synthesis routes were
shown casually. Ammonium-based polymers, a subclass of these polymers, were also demonstrated. It is
beneficial to consolidate the rules for the surface group behavior through the chemical interaction of
Keywords:
Adsorption
their containing polymers. The exploitation of ARP in pollutant adsorption, flocculation/coagulation,
Coagulation and flocculation photocatalysis, and membrane purification was highlighted. Amine groups determine these materials'
Photocatalysis approaches and their performance in the selected applications. Moreover, ARPs differ among themselves
Membrane in their internal structure, which helps to determine the impact of the polymer backbones and forms on
Quaternization the performance of amine and ammonium groups. Hence, the crucial roles of amine/ammonium groups
have been analyzed, indexed, and explained. Perspectives and indicators are introduced that help design
nanomaterials based on these groups to serve environmental purposes. In light of this review, potential
directions for the future with ARPs have been proposed.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction Numerous reviews have addressed nanomaterials in water

Water is one of the essential natural resources on earth. Some
undesirable substances might reach water bodies or ground res-
ervoirs and make them a threat to life and public health. There are
many reasons for this pollution, such as poor sewage treatment,
industrial waste, radioactive waste, heavy metals, and farmland
drains. The World Health Organization (WHO) stated that
approximately 1.7 million people died due to water pollution, and
four billion cases of various health problems were reported annu-
ally due to waterborne diseases [1]. Accordingly, it was stated in a
United Nations report that providing sustainable clean freshwater
is a challenge for the whole world [2]. Concerning Egypt, the World
Bank claimed that the cost estimation of insufficient water supply,
drainage, and hygiene in 2017 was around 1.61% of GDP [3]. Thus, it
has become critical to design and develop nanomaterials and un-
derstand their properties to combat water pollution.
* Corresponding author.
E-mail address: mohamed.halwagy@science.tanta.edu.eg (M.E. Elhalwagy).
treatment in terms of; (1) predominant surfaces including carbon-
based materials [4], polymers [5], metal oxides [6], etc.; (2) appli-
cations including adsorption [5,7], photocatalysis [8], coagulation/
flocculation [9], filtration membranes [10], etc.; (3) nanomaterial
synthesis [11], structure [5,7,12], form, and origin [13]; (4) target
pollutants including organics [5] and inorganics [4,12]; and (5)
active ingredients including functional groups, metallic compo-
nents [14], etc. In addition, it is undeniable that many reviews
address more than one of these facets. However, the latter aspect,
dealing with the crucial role of the surface functional groups, was
rarely reviewed.
By definition, amines are compounds containing at least one
amino group as their functional group. Amines are generally weak
bases in which a nitrogen atom undergoes sp3 hybridization and
binds to one or more carbon atoms. Amine inversion occurs rapidly
at room temperature through a transition state where the nitrogen
hybridization transforms from sp3 to sp2. From this vision, amines
are classified as primary (R
NH2 ), secondary (RR�
NH), or ter-
tiary amines (RR� R��
N) depending on the number of carbon
atoms attached to the hybrid nitrogen atom. On the other hand, a

https://doi.org/10.1016/j.mtchem.2022.101344
2468-5194/© 2022 Elsevier Ltd. All rights reserved.
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
polymer is a long chain of repeating chemical units called a
monomer. The polymer backbone is the most extended series of
covalently bonded atoms that create a continuous molecule. The
term “amine-rich polymers” (ARPs) refers to a class of polymers
defined by their functional groups. An ARP contains a high con-
centration of primary, secondary, and/or tertiary amine groups in
the polymer backbone and/or side branches.
Herein, a survey of ARPs was conducted. The ARPs were classi-
fied based on the origin of their raw materials, whether natural or
synthetic. The chemical structure and key synthesis routes were
demonstrated casually. Then, an analysis of the critical role of
amine groups in pollutant adsorption, flocculation/coagulation,
photocatalysis, and membrane purification was addressed. The
review also deals with transforming the amine groups on the
polymers into quaternary groups. Authentic quaternary ARPs were
also listed and discussed.
2. Bio-based ARP
Biopolymers are made from natural, renewable materials. Bio-
based ARPs are a group of these polymers that contain surface
amine groups densely. This category includes chitosan (CS), poly-
dopamine (PDA), and its analogs, in addition to some polymers of
amino acids (PAAs).
2.1. Chitosan (CS)
CS is a biopolymer derivative comprising N-acetyl D-glucos-
amine and D-glucosamine interlinked by b-1,4eglycosidic bonds
[15], Scheme 1. It is obtained by the alkaline deacetylation of chitin,
a naturally occurring raw material found in crustacean shells. CS is
similar to cellulose, with the hydroxyl group at the C2 position
replaced by an amino group. It also contains two hydroxyl groups in
the C3 and C6 positions. CS is characterized by resistance to germs,
fungi, and viruses in addition to non-toxicity and full biodegrad-
ability. CS also takes different forms, such as flakes, powder, gel
beads, sponges, nanofibers, membranes, and nanoparticles (NPs)
[16].
2.2. Polyamino acids (PAAs)
Amino acids (AAs) have at least two terminal functional groups:
amino and carboxyl, forming polymers through consecutive pep-
tide bonds. One or more AAs might be present in the same polymer
chain. AAs can be any of the twenty genes in the human genome, as
well as unnatural AAs. Upon polymerization, the AAs' functional
groups are transferred to the resultant polymer [17]. Such polymers
exhibit poor mechanical and solubility characteristics due to amide
Scheme 1. N-deacetylation of chitin into CS.
2
Materials Today Chemistry 27 (2023) 101344
bonds. However, pseudo-PAAs utilize non-amide bonds, such as
esters, imino carbonates, and carbonates [18]. The first pseudo-poly
(AAs) polyester was early synthesized from N-protected trans-4-
hydroxy-L-proline. Later, other materials such as serine, hydroxy-
proline, threonine, tyrosine, cysteine, glutamic acid, and lysine
were also used [19]. PAA-based nanomaterials take various forms,
including gels, nanomembranes, nanofibers, nanotubes, micelles,
and vesicles [20e23]. A limited number of PAA polymers contain a
terminal amino group, Scheme 2.
Amino-terminated peptide dendrimers are large molecules
based on radially branched peptide bonds and covalently attached
terminal amine groups. The dendritic peptide comprises three
distinct regions: the core, branching, and terminal groups. Den-
dritic cores could be derived from peptides (e.g., poly-L-lysine) or
polyamidoamine (PAMAM) (Section 3.2.1) [24]. Lysine-based
dendrimers have an excellent reputation for being biodegrad-
able and biocompatible [25]. Typically, L-lysine with protected
amino groups is base-catalyzed to form an amide bond between
the carboxylic group and a core containing a specified number of
amino groups. After unprotecting, the 1st generation is already
established. The surface amino groups are now duplicated.
However, adding new generations is restricted based on the
consequent crowding on increased interactive sites in higher
generations [26]. Despite this, Byrne et al. described the possi-
bility of controlling the number of dendritic arms using dendrites
from the 2nd to the 5th generation of poly (propylene imine) [27]
(Section 3.2.3). Until now, these materials have not been effec-
tively used in water treatment.
2.3. Polydopamine (PDA) and its analogs
b-Arylethylamines are naturally occurring neurotransmitters in
humans and animals. They can be easily synthesized by reducing
aryl -nitroethane or -acetonitriles and their derivatives. The most
famous of these compounds is PDA, formed by dopamine (DA)
oxidation, Scheme 3a. DA oxidation is very easy; it might occur
spontaneously in the air. PDA structure and its analog consist of
quinoid and indoline species. The importance of PDA stems from its
diverse nucleophilic and electrophilic sites gained from the
monomer that enhance its unique ability to cover almost all types
of surfaces. PDA also creates insoluble aggregates that might be
employed independently [28].
Mro
wczyn

ski et al. presented a detailed review describing the
chemistry of PDA analogs [29]. The prominent DA analogs with
functional amine groups are L-dopa, tyrosine, tyramine, norepineph-
rine, 5,6-dihydroxyindole, and 5,6-dihydroxyindole-2-carboxylic
acid, Scheme 3b. Hence, polymerization of one of the DA analogs or
derivatives, post-modification of PDA, and copolymerization with
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay Materials Today Chemistry 27 (2023) 101344

Scheme 2. Amino-rich PAAs originated from proteinic acids.

other monomers could be used to obtain PDA-like polymers. How- 3. Synthetic ARPs
ever, PDA itself has the most significant number of surface amine
groups [30]. PDA analogs make a negligible contribution to removing Synthetic polymers do not exist in nature, either by themselves
pollutants from water. or with their monomers of origin. This category includes many

Scheme 3. (a) Structure of PDA and its analogs; (b) structure of DA and prevailing DA-like monomer.

3
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
polymers, most of which are of fossil origin. Here, synthetic ARPs
will be reviewed in two categories: soluble and insoluble. Poly-
anilines (PANi), poly (phenylenediamine) (PPD), poly (amino sty-
rene) (PAS), and polypyrrole (PPy) are examples of insoluble
polymers. On the other hand, soluble polymers include poly-
amidoamine (PAMAM), polyethyleneimine (PEI), poly (propyle-
neimine) (PPI), poly (allylamine) (PAM), polyvinylamine (PVAm),
and triazine dendrimer.
3.1. Water-insoluble synthetic ARPs
3.1.1. Polyaniline (PANi) and its derivatives
The different forms of redox and doped states of PANi and its
analogs are shown in Scheme 4. Considering PANi, the parent
example (R ¼ 0), leucoemeraldine is the reduced form that con-
tains only a repeating benzenoid diamine ring (x ¼ n). Perni-
graniline, the oxidized form of PANi, has only a repeating quinoid
diamine ring (x ¼ 0). The most stable PANi form is emeraldine,
which has an equal number of both units (x ¼ n=2). The imine and
amine groups could be further protonated or deprotonated
depending on the pH level, yielding a base- and salt-subform for
each PANi oxidation state [31]. It can be inferred that pernigraniline
Scheme 4. Different redox forms and doped states of PANi and its analogs where x is the reduced component, n is the number of the repeating units, and R is a substituted group in
the ortho, meta, or para position. (Redrawn with modification from Refs. [31]).
4
Materials Today Chemistry 27 (2023) 101344
consists of quinonediimine, aminobenzene, and imine linkage. The
quinonediimine component is responsible for the pernigraniline
forms' breakdown. In comparison, the cationic emeraldine form is
commonly utilized as an adsorbent [32].
ANi-derivatives' polymers as well as PANi were made via oxida-
tive polymerization of monomers in alkaline and acidic conditions
[33,34]. The properties of these polymers are utterly different from
those of PANi itself. Perhaps the most prominent differences are the
degree of polymerization, functional groups, surface morphology,
electrical conductivity, and solubility. Considering Scheme 4, the
most frequently seen (R) might be an amino, hydroxyl, nitro, or
carboxyl group in ortho- meta- or para-position.
3.1.2. Poly (amino styrene) (PAS)
Even though amino styrene (Vinyl aniline) is an ANi derivative,
the polymerization process does not rely on the amine group. The
active hydrogen in primary amino groups impedes direct anionic
live polymerization. Hence, the polymer is usually prepared by the
direct nitration of polystyrene, which is then easily reduced to the
amine group. Another route includes protecting the amino group
with dimethyl silane before polymerization in the presence of
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
Scheme 5. Polymerization of amino styrene analogs with syndio-specific catalyst. (Redrawn with modification from Ref. [35]).
syndio-specific catalyst systems [35]. The primary amino groups
were recovered by hydrolysis followed by neutralization, Scheme 5.
Poly (tertiary 4-aminostyrene)s were made by anionic live poly-
merization of related monomers in THF at
78  C with cumyl cesium
as an initiator [36]. Early on, the polymer isomer containing the
amino group at the meta-position was also synthesized by free
radical bulk polymerization of 3-nitrostyrene. These polymers belong
to a semi-crystalline polymer class that includes poly (4-
aminomethyl styrene) and poly (4-aminoethyl styrene). Their
melting temperatures are much higher than polystyrene itself. The
enhanced crystallization, solubility, and melting temperature are al-
ways justified by hydrogen bonding between the amine groups [35].
3.1.3. Polypyrrole (PPy)
PPy is a heterocyclic cationic conductive ARP with non-toxic and
biocompatible properties suitable for electronic and environmental
applications. The polymer was obtained in various nanoforms such
as particles, tubes, fibers, films, and sponge-like structures [37e42].
The conjugate backbone of PPy, responsible for its conductive
properties, could be described in oxidized and reduced form,
Scheme 6. The reduced form of the PPy is the insulator form, unlike
the oxidized version.
Scheme 6. Oxidized and reduced forms of PPy.
5
Materials Today Chemistry 27 (2023) 101344
PPy's oxidative polymerization might occur chemically, elec-
trochemically, or by ultrasonic vibrations. Moreover, it might be
made using electrospinning, microemulsion polymerization,
mechanochemical polymerization, and photopolymerization. Still,
PPy's polymerization is carried out in organic solvents and acidic
aqueous environments with FeCl3, ammonium persulfate, or other
oxidizing agents. It could produce vast quantities of PPy in various
forms. On the other hand, ultrasonication polymerization includes
quick response time, low cost, scalability, and the ability to produce
homogenous PPy with constant shape, size, and conductivity. It is
recommended to check Pang et al.'s review on the synthesis of PPy
and the factors affecting its conductivity [43].
3.2. Water-soluble synthetic ARPs
3.2.1. Polyamidoamine (PAMAM)
Dendrimers are highly symmetric nanosized particles that grow
radially from the internal core forming a homogeneous nano-
structure. The outer shell contains a functional group that might be
identical or different from the dendrimer's inner-arms groups.
Tomalia and coworkers report the first synthesis of PAMAM den-
drimers. PAMAM dendrimers, as well as others, could be synthesized
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
using divergence and convergence approaches. In a divergent
approach, dendritic polymers are built up through nonlinear growth
from the core. Tomalia synthesized a branched ester-terminated core
through the Michael addition of methyl acrylate to ammonia. Sub-
sequent repeating amidation with ethylenediamine (EDA) and Mi-
chael's addition to methyl acrylate generated the amine-terminated
PAMAM dendrimers [44], Scheme 7. In the convergent strategy,
branches are first constructed based on the previous chemical re-
actions and then connected to a central core. PAMAM dendrimers
bear a large number of functional groups. Primary amines represent
the exterior surface, whereas amide and tertiary amines form the
inner branching [45]. Recently, Lyu et al. presented a review of the
PAMAM dendrimers. The study included covalent and supramolec-
ular synthesis, alternative cores, and terminal chains [46].
3.2.2. Polyethyleneimine (PEI)
Gleede et al. studied the chemistry of aziridines and their de-
rivatives as building blocks for polyamines through ring-opening
polymerization [47]. PEI is one of these polyamines; it is a
repeating polymer composed of an amine group and two aliphatic
carbon atoms. Such polymers come in several structures, including
linear, branched, and dendrimer, Scheme 8. Linear PEI could be
synthesized by the cationic ring-opening polymerization of
substituted 2-oxazolines and subsequent acidic hydrolysis [48,49].
The resultant polymer is solid at room temperature with a
repeating unit of secondary amine attached to ethylene. There are a
few terminal primary amine groups, but they are not numerically
comparable to the secondary groups.
The branching PEI is synthesized via aziridine cationic ring-
opening polymerization. The number of secondary amines in the
branched polymer equals the sum of the primary and tertiary
amine groups. However, the proportion of the primary groups in-
creases with increasing the polymer molecular weight (Mwt) [50].
The branched structure is liquid at room temperature, with
Scheme 7. Schematic representation of PAMAM synthesis and its molecular structure. (Redrawn with modification from Ref. [46]).
6
Materials Today Chemistry 27 (2023) 101344
different amine groups distributed regularly [51]. On the other
hand, Yemul synthesized PEI dendrimers using EDA as a starting
core. Initially, the amine groups were reacted to vinyl bromide in
methanol using a Michael addition reaction. The terminal bromide
was then converted into amine groups using the Gabriel method,
which involves two consecutive reactions with potassium phtha-
limide and hydrazine chloride. The previous steps were repeated
until the 4th generation [52].
3.2.3. Poly (propyleneimine) (PPI)
€ gtel et al. synthesized the first PPI dendrimers. The prepara-
Vo
tion was based on repetitive Michael's addition of an amine to
acrylonitrile. The surface primary amine groups were created by
the subsequent reduction of the nitrile groups. The most popular
cores used are EDA and 1,4-diaminobutane (DAB) to initiate den-
drites up to the 5th generation, Scheme 9 [53,54].
3.2.4. Poly (allylamine) (PAM)
PAM is a cationic polymer made by radical or cationic poly-
merization of allylamine. The polymer side chain comprises pri-
mary amine groups, while the backbone contains no nitrogen [55].
Allylamine polymerizes very slowly to form oligomers or short-
chain polymers. This degradative chain transfer arises from the
radical self-stabilization through resonance, while hydrogen pro-
vided by the allylamine monomer is involved in rapid termination
[56,57]. Various complexation agents were used to decrease the
degradative chain transfer to improve the polymerization yield and
polymer Mwt. Recently, Sepehrianazar and Guven reinvestigated
the microstructure and Mwt of PAM in different protonic acids. The
Mwt of the polymer produced from the allylamine salt follows the
order of H3PO4, H2SO4, and HCl, Scheme 10. Moreover, the latter has
a Mwt higher than that of the deacidified form [58]. PAM is only
soluble in water and methanol and is insoluble in all other solvents.
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay Materials Today Chemistry 27 (2023) 101344

Scheme 8. Structures of PEI linear, branched, and dendrimer forms.

3.2.5. Polyvinylamine (PVAm)
PVAm is a simple-structured polybase water-soluble polymer.
Although the direct monomer is stable, polymerization is usually
carried out via intermediate polymers. PVAm is often obtained
from the free radical polymerization of N-vinylformamide, the
most prevalent intermediate, followed by hydrolysis, Scheme 11a
[59,60]. The Hoffmann degradation of polyacrylamide could also
yield the polymer; the last route is the least fortunate, Scheme 11b
[61]. The polymer is typically isolated and stored as the hydro-
chloride salt to be protected against atmospheric carbon dioxide.

Scheme 9. Master scheme of PPI dendrimers synthesis. (Redrawn with modification from Ref. [53]).

7
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay Materials Today Chemistry 27 (2023) 101344

Scheme 10. Linear and crosslinked structures of PAM and their acid complexes. (Redrawn with modification from Ref. [58]).

Scheme 11. Synthesis routes of PVAm (a) radical polymerization of N-vinylformamide; (b) Hoffmann degradation of polyacrylamide. (Redrawn with modification from Ref. [60,61]).

8
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
The hydrochloride salt is also soluble in water but insoluble in other
polar solvents such as methanol or ethanol [62]. PVAm is a strong
polyelectrolyte (PEL) since it is partially ionized over the working
pH scale. This behavior results from the mutual interaction be-
tween neighboring amine groups [63].
3.2.6. Triazine dendrimer
Triazine dendrimers are a group of radially branched com-
pounds composed of trichlorotriazine core, spacers, and surface
groups, Scheme 12a. The distinguished properties between these
polymers depend on the surface groups, whether amine, hydroxyl,
carboxyl, or others. The chloride group on trichlorotriazine is usu-
ally replaced by a two-amine terminated spacer with one of the
amine groups protected. The reaction depends on the temperature
and the number of substituted chloride groups, Scheme 12b. Upon
reaching the generation of interest, a compound with a terminal
amine and the target group on the other end is then introduced
[64]. A convergent strategy might also synthesize triazine den-
drimers [65]. Amine-terminated triazine dendrons are rarely used
in water treatment due to their complicated synthesis.
4. Ammonium-based polymers
Ammonium-based polymers contain a quaternized nitrogen
atom either in the side chain or in the polymer backbone. The ni-
trogen with four alkyl groups and a permanent positive charge
(NRþ4 ) is called a quaternary ammonium cation. The attached anion
Scheme 12. (a) Schematic structure of triazine dendrimer of 2nd generation; (b) Chlorotriazines reactivity depending on reaction temperatures.
9
Materials Today Chemistry 27 (2023) 101344
is usually a halide or sulfate, forming a quaternary ammonium salt.
Quaternary ammonium polymers are ionized in solution to form a
cation with disinfectant, enhanced solubility, and ion exchange
characteristics. The disinfectant properties arise from the positive
charge that makes them bindable to the microbes' surfaces with the
opposite charge [66].
Examples of this class of polymers include poly (dia-
llyldimethylammonium) (PDADMAC) and poly (epichlorohydrin-
dimethylamine) (EPI-DMA), Scheme 13 [67]. PDADMAC has a cyclic
backbone formed by DADMAC's unique cyclopolymerization. The
polymer is very hydrophilic, whereas the permanently charged
quaternary ammonium groups contribute to its high water solubility
[68]. Epichlorohydrin is polymerized with a secondary amine, such
as dimethylamine, in concentrated aqueous solutions at high tem-
peratures. The resulting polymer is structurally distinct from almost
all other PELs where the cationic charges are located throughout the
backbone chain rather than in pendant side chains [69].
5. Quaternization of ARPs
Quaternization of the ARPs involves the introduction of an
additional bond to the central N-atom of the amine group, where
the latter is permanently transformed into sp3 hybridization. The
newly formed quaternary ammonium groups have the maximum
spacing between the substituents on the nitrogen with a perma-
nent positive charge as the amine inversion was inhibited [70]. The
main advantage of the quaternization of ARPs is that the main
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
Scheme 13. Structure of PDADMAC and EPI-DMA ammonium-based polymers.
backbone is preserved. Thus, a modified polymer has properties
depending on the alkyl group length.
Quaternization of the ARPs can be obtained directly or indirectly
[91]. The direct method involves converting the polymer amino
groups to quaternary ammonium groups. Another direct approach
includes polymerizing quaternized monomers [92]. In contrast, the
indirect method involves attaching a side chain containing a qua-
ternary ammonium group via the pre-existing amine group. Ciej-
ka's work is a comprehensive example of direct and indirect
quaternization reactions. Under basic conditions, direct PAM qua-
ternization was used to obtain an N-methylated derivative through
reductive methylation with CH3I, Scheme 14a. The second direct
route included successive alternant steps of N-alkylation with an
aldehyde (e.g., hexanal) and subsequent reduction with sodium
borohydride, followed by CH3I methylation (not shown), Scheme
14b. Finally, the indirect quaternization included the reaction of
PAM with glycidyltrimethylammonium chloride (GTMAC) in water
at 57  C to obtain poly [(3-allylamino-2-hydroxypropyl)-trimethy-
lammonium chloride] [89], Scheme 14c. Selected examples for ARP
quaternization are shown in Table 1.
6. Advanced spectroscopy for ARP
Advanced spectroscopy for ARP plays multiple roles in water
treatment applications. On top of these roles are traditional char-
acterization, amine group density, and amine group tracking before
and after contamination contact i.e., mechanism analysis. Notably,
density functional theory (DFT) and molecular simulation have also
been utilized to gain a deeper understanding of the interaction
between surfaces and pollutants. The advantage of theoretical
calculations is that they provide crucial information for under-
standing the molecular-level interaction mechanism, such as
binding energy, bond distance, kinetic process, etc. The majority of
this information is difficult to obtain through experimentation.
6.1. Surface/bulk amino density
The density of the amine groups is a crucial surface property. It
provides clarification about loading kinetics and thermodynamics
studies of the surface's amination in addition to nanocomposites'
behavior and nanotoxicity. Hence, a reliable method is usually
required to determine the densities of the immobilized amino
groups. There is no generally accepted method for such quantifi-
cation [93,94]. This might be due to the differences in the surface's
10
Materials Today Chemistry 27 (2023) 101344
nature, amines, loading range, and binding style. Also, some diffi-
culties arise from distinguishing between the surface and bulk
amine groups.
In general, “destructive” and “non-destructive” approaches are
usually utilized to assign surface amine density. In the destructive
approach, the amine is chemically and/or physically decoupled from
the surface before being analyzed using various techniques. In this
instance, the measured amine density is typically lower than the
actual loading, with the loss percentage depending on the efficacy of
the decoupling method and steric hindrance that restricts the acces-
sibility of the reagents. However, the approach usually reports the total
amine density, i.e., surface and bulk amine. In the non-destructive
approach, the amino groups remain attached to the surface, and
their assignment is made either directly or indirectly. Most of these
methods report on the accessible surface rather than bulk amines.
Colorimetric and fluorometric spectroscopies with labelling
steps are examples of the nondestructive method. For instance,
Samantha et al. produced aminated biocompatible polyethylene
terephthalate films through an aminolysis reaction with ethyl-
enediamine or PVAm. The number of primary surface amine groups
was quantified colorimetrically using the electrostatic interactions
between the positively charged amino groups and the anionic Or-
ange II dye in an acidic solution. Under alkaline conditions, the
neutral amino groups released Orange II molecules into the solu-
tion. The absorbance of the released dye was measured with an UV-
spectrometer and correlated to the CeNH2 content derived from X-
ray photoelectron spectroscopy (XPS). XPS was chosen as the
comparison technique because it can identify the surface elemental
composition and valence for penetration depth in the order of
10 nm in a nondestructive manner [95].
In contrast, carbon-hydrogen-nitrogen (CHN) combustion
analysis, nuclear magnetic resonance (NMR), mass spectroscopy,
and atomic spectroscopy were used to estimate the total amine
densities as typical examples of destructive methods [94]. For
instance, the degree of CS deacetylation (DD) refers to the ratio of
the acetyl groups that were converted to amine groups during the
CS-chitin conversion. By definition, DD directly expresses the
density of amine groups on the CS constituent. As DD increases, a
strong repulsion of immobilized charges occurs, and the viscosity
decreases in addition to the ascending solubility in acidic aqueous
solutions [96]. Jianhui et al. dissolved CS at a concentration of
10 mg/mL in D2O/DCl (1%), and then 1H NMR was used for quan-
titative evaluation of the de-protonatable functional groups. After
that, CS DD was calculated according to Eq. (1) [97].
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay Materials Today Chemistry 27 (2023) 101344

Scheme 14. Quaternization of PAM (a) and (b) represent direct approach; (c) indirect approach. (Redrawn with modification from Ref. [89]).

Table 1
Selected examples for ARP quaternization.

Target ARP Method Reagents Ref.

Chitosan Indirect GTMAC [71,72]

Chitosan Direct NaOH, Methyl iodide and NaI [73]
ε-poly-L-lysine Direct Alkyl halide (n ¼ 1,2,4) [74]
Poly (dopamine) Indirect GTMAC [75]
Polyanilines Direct Methyl iodide [76]
Polyanilines Direct Hexyl bromide [77]
Polypyrrole Direct Iodoalkane (I-CnH2nþ1, n ¼ 1,3,5,7,10) [78]
Polypyrrole Direct Diiodine with different numbers of carbon atoms for quaternization and crosslinking reactions [79]
Polyamidoamine Direct Bromoalkane (I-CnH2nþ1, n ¼ 2,8,12) [80,81]
Polyamidoamine Direct 2-chloroethyl isocyanate, N,N-dimethyldodecylamine [82]
Polyethyleneimine Direct Bromopropane [83]
Polyethyleneimine Direct Formaldehyde, Formic acid, Methyl iodide [84]
Poly (propyleneimine) Indirect GTMAC [85,86]
Poly (propyleneimine) Direct Methyl iodide or chloride [87]
Poly (propyleneimine) Direct Acetyl chloride and MeI [88]
Poly (allylamine) Direct NaOH, Methyl iodide, NaI [89]
Poly (allylamine) Direct NaOH, hexanal [89]
Poly (allylamine) Indirect GTMAC [89]
Polyvinylamine Direct Polymerization of N-methyl-N-vinylformamide [90]

11
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay Materials Today Chemistry 27 (2023) 101344

transfer from the aqueous phase to the solid substrate, forming a

1
HD
DDð%Þ ¼ 1  100
HD þ ðHAC =3Þ
where 1 HD and HAC are the peak integrals of the deacetylated
monomer anomeric proton and the three protons of the N-acetyl
group, respectively. Generally, the nondestructive methods were
typically 20e30% lower than those measured by the destructive
assays, as the former method estimated the surface amine only [98].
6.2. Mechanism analysis
Spectroscopic techniques such as XPS, Fourier transform
infrared (FTIR), Raman and X-ray absorption fine structure (XAFS)
have typically been applied to ARP nanomaterials prior to and after
interaction with pollutants. The popping up and down peaks, their
disappearance, intensities, position, and position shifting might
provide useful information regarding the interactions between
amino groups and pollutants [8].
To clarify, Xueqi et al. synthesized a nanofiber cross-linked
hydrogel network based on nitrogen-doped carbon dots and cel-
lulose using an ecologically friendly low-temperature hydrother-
mal technique. Then a second layer of a CS network was formed
using solvent replacement [99]. The resulting gels exhibited sig-
nificant adsorption capabilities of 148.30 mg/g for Cu(II) and
294.46 mg/g for Cr(VI). FT-IR and XPS measurements were con-
ducted before and after the adsorption of heavy metal ions. After
Cu(II) and Cr(VI) adsorption, the gel's NeH and OeH stretching
vibration band at 3432 cm
1 was reduced and moved to 3396 and
3355 cm
1, respectively. Moreover, the distinctive glucopyranose
ring band at about 1100 cm
1 was considerably diminished. This
revealed that both hydroxyl and amino groups were engaged as
adsorption sites for the selected heavy metal ions. According to XPS
studies, the N 1s spectrum shifted from 398.8 to 399.4 eV, and the
intensity of the amino peak decreased significantly. The latter is
conclusive evidence that the amine group's pair of electrons were
coordinated with metal ions.
7. The crucial role of ARP in water remediation
7.1. Adsorption
Liquid-solid adsorption is a separation process usually applied
to extract contaminants from water. In this process, the pollutants
surface layer(s) [100]. The type and density of superficial groups
(1)
both play essential roles in determining the mechanism and ca-
pacity of adsorption. Numerous adsorption mechanisms, including
electrostatic interactions, ion exchange, hydrogen bonding, chela-
tion, and complexation, might be attributed to amine groups in the
polymer structure. On the other hand, organic rings within the
same structure might facilitate adsorption via pep and dipole-
dipole interactions [101].
This review is not concerned with comparing various ARPs but
instead analyzes the function of the amine group itself. However, it
is helpful for the reader to realize the magnitude of their difference
in the adsorption process. Table 2 provides comparative examples
of dye adsorbents based on ARPs and magnetite (Fe3O4). The
following will discuss the different roles provided by the amine
groups on the surface of polymers in the adsorption process.
7.1.1. Cationic behavior
The nitrogen in heterogenized amines is connected to two
hydrogen atoms, alkyl groups, or a hybrid of these groups. Moreover,
it has a lone pair of unpaired electrons with an electron density area
around the nitrogen atom. The electron density and the nitrogen's
electronegativity result in a partial negative charge at that site.
Hence, the hydrogen ion of the acid medium can associate with the
N, resulting in a positive charge. This cationic behavior allows it to
absorb organic and inorganic negatively charged pollutants elec-
trostatically. Cationic behavior depends on the Zeta-potential of the
surface and pH of the solution. The surface gets more charged as the
pH drops below the isoelectric point and vice versa, Scheme 15.
Electrostatic attraction cannot be used to explain the adsorption of
negative contaminants at pH values greater than the isoelectric
point. Quaternization of ARP could shift the isoelectric point to a
higher pH level, extending the cationic response [111].
For instance, Diclofenac sodium is an anti-inflammatory drug that
causes an environmental problem when it seeps into natural water
sources. Jiang et al. synthesized pEPI-DMA hydrogel by crosslinking
copolymerization as a new adsorbent to remove aqueous diclofenac.
The adsorption capacity of the hydrogel gradually decreased as the
pH of the solution increased from 3 to 10. According to the Langmuir
fitting model, the adsorption capacity could reach 540.3 mg/g,
significantly greater than reported adsorbents. Adsorption mecha-
nisms include the electrostatic attraction between the quaternary
ammonium cation and negatively charged diclofenac, along with the
formation of hydrogen bonds in which hydroxyl groups might also

Table 2
Illustrative examples of dye adsorbents nanomaterials based on magnetite and ARPs.

Adsorbent Pollutant Type qe;max (mg/g) Optimum Condition Ref.


Time (min) Adsorbent dose (g/l) Pollutant dose (mg/l) Temp. ( C) pH

Fe3O4/CS Methyl Orange Anionic 638.6 360 0.1 200 29.85 4 [102]
Fe3O4/CS Methylene blue Cationic 0 e e e e e [102]
Fe3O4/poly-lysine Methyl blue Anionic 318.47 30 1 200 e 2 [103]
Fe3O4/PDA Methylene blue Cationic 10 360 0.5 6 e 7 [104]
Fe3O4/PDA Methyl Orange Anionic 2.97 360 0.5 6 e 2 [104]
Fe3O4/PDA Rhodamine B Cationic 195.3 40 0.4 20 24.85 7 [105]
Fe3O4/PANi Basic Blue 3 Cationic 78.13 60 0.1 50 30 10 [106]
Fe3O4/PANi Acid Blue 40 Anionic 216.9 50 0.1 100 30 5.5 [107]
Fe3O4/PPy Brilliant green Cationic 263.85 20 1 320 30 e [108]
Fe3O4/PPy Eosin Y Anionic 226.76 20 1 320 35 e [108]
Fe3O4/PPy Methyl orange Anionic 152.91 45 1 320 35 e [108]
Fe3O4/PEI Crystal violet Cationic 372.6 90 1 700 24.85 8 [109]
Fe3O4/PEI Congo red Anionic 325 10 1 350 25 3 [110]

12
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
Scheme 15. Surface amine group response at different pH levels relative to the isoelectric point.
participate. After five rounds of regeneration, the adsorption capacity
remained at 80.32%. Furthermore, the pEPI-DMA hydrogel could
selectively adsorb diclofenac from mixed systems of quinolone and
tetracycline [112].
Celestino et al. charged hydrophilic bentonite nano-clay with
PDADMAC to remove aqueous gallic acid. Gallic acid possessed a
negative charge in an acidic environment, whereas the quaternary
amine group of the combination gave it a cationic character. As a
result, the large adsorption capacity of 238.45 mg/g was attribut-
able to the attractive electrostatic interactions between opposing
charges [113].
Zhou et al. mixed the (3-Aminopropyl)triethoxysilane modified
fly ash with a 37.5%w/w pEPI-DMA. The upgraded cationic fly ash
contained 7.2 wt% of the cationic polymer. According to Zeta-
potential analysis, the composite maintained a positive potential
over a pH range of 3e11. Electrostatic attraction arose between the
cationic ammonium groups and anionic reactive black 5 and reac-
tive red 239 dyes. In addition, hydrogen bonds were established
between the surface hydroxyl groups and nitrogen atoms within
these azo dyes. The maximum loading capacities were 146.2 and
124.8 mg/g, respectively, which is 1.5 times that of commercial
activated carbon [114].
PPI dendrimers-based nanocomposites showed outstanding
adsorption toward metal ions [115e117]. For instance, Hayatia and
colleagues synthesized PPI dendrimers up to the 4th generation.
The PPI was then refluxed with surface-acylated carbon nanotubes
(CNTs). The resultant PPI/CNTs nanocomposite was used to remove
metal ions from water. At acidic pH, the limited adsorption of these
heavy metals was ascribed to electrostatic repulsion between the
cationic amino group and the heavy metal ions. However, the
adsorption increased steadily with the increase in the pH level of
the solution. The optimal adsorption capacities were 2000 mg/g for
Hg(II), 1750 mg/g for Pb(II), and 1650 mg/g for Ni(II) at pH ¼ 7 [117].
Xu et al. created poly (m-phenylenediamine) (PmPD) via
laccase-catalyzed enzymatic polymerization for heavy metal
adsorptive removal. The polymer showed adsorption capacities for
Cu(II), Pb(II), and Cr(III) with values of 556, 526, and 476 mmol g
1,
respectively [118]. Meng et al. used carbon dots combined with poly
(o-phenylenediamine) (PoPD) for the same purpose. The adsorp-
tion was inhibited by amino group protonation with (Hþ) from the
medium at low pH levels. However, as the pH went higher, the
adsorption capacities might reach 48.88 mg/g for Cu(II), 53.44 mg/g
for Pb(II), and 36.20 mg/g for Cd(II) [119].
Cui and others reported that the sorption capacity of Cr(VI) by
PAMAM surrounding the magnetic silica particles (Fe3O4@-
SiO2ePAMAM) increased with the succession of generations until
13
Materials Today Chemistry 27 (2023) 101344
the 3rd generation (334.45 mg/g) and then returned to deteriorate
at the 5th generation. Interestingly, increasing the number of
PMAMA generations does not continuously improve, if not worsen,
the adsorption process. The advanced generations hindered the
contact of chromium ions with the amine groups present within
PAMAM. Batch adsorption experiments revealed that equilibrium
was attained in 60 min and that the ideal pH value was 3. The
adsorption was attributed to the electrostatic interaction between
the protonated amine and predominant anions (Cr2 O2

7 and
HCrO

4 ) at that pH level [120].
7.1.2. Coordination/complexation sites
Functional amine groups might interact with metal ions through
different mechanisms depending on the metal, pH, and solution
matrix. One of the most important mechanisms is the formation of
coordination bonds based on a pair of electrons on the nitrogen
atom [121]. It became a plausible explanation for the adsorption of
cationic metal forms on the amine groups with cationic behavior.
For instance, Abukhadra et al. integrated CS chains with meso-
porous silica (MCM-48) for the removal of radioactive U(VI) and
Sr(II) ions from water. The composite showed promising retention
removal capacities of 261.3 mg/g for U(VI) and 328.6 mg/g for Sr(II).
At a given pH, the valency of the dominant metal ion determines
adsorption efficiency. Electrostatic attraction cannot be relied upon
since the U(VI) and Sr(II) ions take multiple positive forms in the pH
range of 2e8. This suggested that the adsorption mainly occurred
due to complexation, particularly in the presence of amine groups
with a lone pair of electrons [122].
7.1.3. Hydrogen bonding
A hydrogen atom covalently bound to an extremely electro-
negative atom (e.g., N, O, or F) has a partial positive charge, while
this electronegative atom has a partial negative charge. Then, a
hydrogen bond is formed by the dipole-dipole attraction within the
same or between different molecules. In the absence of electro-
static attraction, hydrogen bonding is a common explanation for
the adsorption of large molecules.
Minisy et al. applied a CS/PANi hybrid to remove both anionic
and cationic dyes. The nanostructured hybrid showed maximum
adsorption of 240.4 mg/g of anionic Acid Green 25 at pH ¼ 4 and
81.3 mg/g of cationic methylene blue (MB) at pH ¼ 11. The amine
groups of both the PANi and CS chains were protonated in acidic
conditions, resulting in a positively charged surface. Electrostatic
attraction arose between the hybrid and the Acid Green 25 anionic
dye. The surface charge decreased as the pH level increased;
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
hydrogen bonding became the dominant adsorption mechanism. In
comparison, the cationic dye adsorption capacity increased as the
solution's pH increased. Above pH ¼ 9, the hybrid was negatively
charged to remove MB effectively [123].
In another instance, Senguttuvanan et al. performed the
chemical oxidation of pyrrole in the presence of zeolite. This inte-
grated composite targeted the adsorption of reactive red and
reactive blue dyes as models for organic pollutants. The maximum
adsorptions were 122.32 and 116.53 mg/g for reactive blue and
reactive red at an alkaline medium (pH ¼ 9). The anionic dyes were
never expected to be effectively adsorbed in an alkaline medium
where the amine groups lose their cationic nature. The anomalous
pH response was attributed to (1) hydrogen bonding between
amino groups and dyes, (2) interaction between (SO
3 ) and (eNH)
group, and (3) hydrophobic interaction between dyes and com-
posite [124].
Yang et al. modified nanocellulose with PVAm for the adsorption
of chlorpyrifos, a thiophosphate pesticide, from an aqueous solu-
tion. The aqueous crystalline nanocellulose was incubated with
NaOI4 for 48 h at 40  C in the dark for the cellulose ring opening.
PVAm was added and stirred for 24 h at room temperature to
ensure a bond was formed with the opened rings. The resulting
microgel exhibited a chlorpyrifos adsorption capacity of 98.12 mg/
g. The microgel's hydroxyl and amino groups were likely to help
chlorpyrifos be adsorbed by hydrogen bonding and electrostatic
attraction [125].
7.1.4. Anion-exchange behavior
PPy dopants are negative ions that originate mainly from the
anionic moiety used in the synthesis unless they are replaced. Due
to the high mobility of these dopants on the polymer matrix, they
are responsible for the PPy anion exchange behavior [126]. Fenk
et al. introduced a chemical insight into the anion exchange
behavior of PPy based on XPS spectra before and after adsorption.
They synthesized PPy samples doped with mono- and di-dopants
(Cl
, SO2

4 ) were used for fluoride anion exchange. Adsorption
tests showed that mono-dopant PPy has four times the adsorption
capacity (13.98 mg/g) of dual-dopant PPy (3.08 mg/g). After
adsorption, the peak variations indicate that anion exchange
occurred only over (¼Nþ) rather than (eN ¼ ) and (eNHe) with the
exchange sequence of ðF
> Cl
> Br
> SO2

4 Þ [127].
Nesterov et al. synthesized PAS and its derivative poly [N-(2,3-
dihydroxypropyl) aminostyrene] from plain polystyrene through
nitration, reduction, and glycidol treatment. A comparative study
was conducted on the ability of the as-prepared polymers to bind
aqueous B(III) ions. The polymers bound boric acid via an ion-
exchange mechanism in the acidic medium. With increasing pH,
the sorption capacity of poly [N-(2,3-dihydroxypropyl) amino-
styrene] increased significantly over PAS. The deprotonation of the
PAS amino groups at high pH levels resulted in a significant drop in
anion-exchange sites. Furthermore, the complexing power of the
vicinal hydroxyl groups of poly [N-(2,3-dihydroxypropyl)amino-
styrene] toward the monoborate ion (BðOHÞe 4 ) was increased [128].
Recently, fiber balls of uniform shape were loaded with PPy for
aqueous Cr(VI) adsorption. The loading procedure included stirring
the fiber balls for 12 h with FeCl3 and pyrrole. The maximum
adsorption capacity was 86.74 mg/g compared to 5.73 mg/g
assigned to plain fiber balls, confirming the essential role of the PPy
in Cr(VI) adsorption. The N-atoms were protonated under acidic
conditions, creating an electrostatic attraction with the acidic
dominant hydrogen chromate anions (HCrO
4 ). Moreover, the N
atoms were deprotonated in the alkaline medium, generating a
charge repulsion between the surface and the dominant chromate


form (CrO2

4 ). However, the chloride ion (Cl ) was exchanged with
14
Materials Today Chemistry 27 (2023) 101344
the chromate anions; consequently, the adsorption filtrate became
cloudy once treated with AgNO3 droplets. In the XPS spectra, the
deteriorated nitrogen peak area after adsorption was explained by
the engagement of nitrogen in the removal of Cr(VI) [129].
D301, a basic ion exchange resin, was stirred with a solution of
0e10% pEPI-DMA to form a D301/pEPI-DMA composite. The
resulting composite's adsorption characteristics toward Cr(VI) were
investigated, with a maximum uptake of 194 mg/g. The adsorption
mechanisms were attributed to ion exchange induced by the
displacement of Cl
from pEPI-DMA and the removal potential
induced by the electrostatic attraction of D301 amino and the
quaternary ammonium group embedded in pEPI-DMA [130].
Functionalization of the D301 resin through in-situ polymerization
of the pEPI-DMA was also conducted for the same purpose. The
latter route improved the surface area and charge density, shifting
the maximum adsorption to 298 mg/g [131].
Additionally, heterogenized PDADMAC was used to remove
dissolved anions. For example, the quaternary ammonium polymer
was used to modify biochar to recover orthophosphate (PO4
P).
The capacity of biochar treated with PDADMAC was about 100
times that of untreated biochar. After phosphate sorption, the N1s
XPS spectra of PDADMAC-treated biochar remained unchanged in
position and intensity, showing that the quaternary N was not
electronically disturbed and that adsorption occurred predomi-
nantly through ion exchange [132].
7.1.5. Trap pollutant molecules
Dendrimer's structure showed improved physical and chemical
properties over conventional linear polymers. Dendrimer solutions,
for example, have a considerably lower viscosity than linear poly-
mers. Numerous chain-ends contribute to the compound's solubi-
lity, miscibility, and reactivity. Due to their spherical shape and
internal cavity, dendrites can also encapsulate adsorbate molecules
within their macromolecule interiors [133].
For instance, Sultana et al. added 2%wt of 3rd generation PPI
dendrimer to the electrospinning solution of the Nilon-6 polymer.
The nanofiber was used for the adsorptive separation of acid red
252 anionic dye. The first 2 min accounted for more than 90% of the
removal. The removal percentage was raised to 99% after 60 min of
contact with acid red 252 dye (100 ppm) by the nanofibers (0.1 g) at
pH ¼ 4. Typically, when exposed to an acidic medium, the terminal
amine groups on polyamide chains and those in PPI dendrimers
acquire a positive charge, emphasizing electrostatic attraction as a
primary mechanism. Additionally, the average diameter of the PPI
dendrites increased due to the repulsion between the charged
amine groups. As a result of the larger cavities, the PPI modifier's
ability to trap and encapsulate anionic molecules increased [134].
7.1.6. Reductive adsorption
The polymer's role might include metal ion reduction after the
adsorption. Some authors reported that the lone electron pair of
nitrogen was responsible for the redox reaction as they noticed a
significant decrease in the quinoid imine ratio (¼N-), in contrast to
the benzenoid amine ratio (-N-) [129,135e137].
Mdlalose et al. synthesized poly (p-phenylenediamine) (PpPD)
using well-known oxidative polymerization techniques. The ob-
tained polymer showed a maximum adsorption capacity of 49 mg/g
towards Cr(VI). The bare PpPD, XPS N1s spectrum, has two high-
resolution peaks at 399 eV for (eNH) and 402 eV for (eNþ), with
molar ratios of 47.8 and 52.2, respectively. After Cr(VI) reductive
adsorption to Cr(III), the oxidation status of PpPD improved, as
evidenced by an increase in the oxidized imine (-N ¼ ) band of 2.7%
at pH 8 and 6.3% at pH ¼ 2, as well as a decrease in the FT-IR
benzenoid peak at 1510 cm-1. Furthermore, the detected XPS
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
bands at 577e578 eV and 586e588 eV correspond to the Cr(III):
Cr2p3/2 and Cr2p1/2 orbitals, respectively [137].
Bao et al. used Schiff-base reactions to bridge amino-
functionalized GO and PAMH. The resulting PAMH-GO composite
had a high capacity of 373.1 mg/g for Cr(VI) adsorption. The
removal mechanism involves an electrostatic attraction between
metal anions and the N-containing groups of PAMH. Furthermore,
the XPS studies suggested that the Cr(VI) ions were partially
reduced to Cr(III) by electron-donating amino groups before che-
lation. Even after ten adsorption-desorption cycles, the PAMH-GO
retained 91.8% of its removal efficacy [138].
Deng et al. synthesized a MnO2/Tannic acid/PEI composite for
metal ions adsorption, Cu(II) and Cr(VI) in particular. The composite
displayed a dendritic structure that provided metal ions with hy-
droxyl and amine sites for complexation. MnO2/Tannic acid/PEI had
maximal adsorption capacities of 121.5 and 790.2 mg/g for Cu(II)
and Cr(VI), respectively. When the adsorbed chromium Cr(VI) was
exposed to the hydroxylamine system, it was converted to the less
hazardous Cr(III) [139].
Wang et al. report that the amine group was responsible for
Pd(II) adsorption over PEI/chitin bio-adsorbent. The coordination
bond with the amine group was confirmed by shifting amino
groups N1s XPS spectra to higher binding energies. Both Pd (0)
(337.59 and 342.69 eV) and Pd(II) (338.28 and 343.53 eV) peaks
were observed, indicating that a reduction reaction took place
during the adsorption process [140].
7.1.7. Associate different layers
Besides providing surfaces with functional groups, ARP has been
used as a laminate between multiple surfaces. Mussel-inspired
chemistry, particularly the versatile coating capability of PDA,
might be used as a functional coat/link for several applications
[141]. Yu et al. modified agarose hydrogel beads (2e4 mm) adsor-
bents with positively charged poly (allylamine hydrochloride)
(PAMH) and negatively charged poly (L-dopa) with different molar
ratios. The hydrogel beads were used for the removal of aqueous
ionic pollutants. The maximum adsorption for Pb(II), Cd(II), and
Cu(II) ions in hydrogel beads with a poly (L-dopa) to PAMH molar
ratio of (3.5:1) was 1625, 657, and 388 mg/g, respectively. The
hydrogel beads with (3.5:1) and (1:3.5) molar ratios showed
maximum adsorption capacities of 467 mg/g for cationic MB and
870 mg/g for anionic methyl orange (MO) dyes, respectively. The
resultant hydrogel might be readily regenerated for reuse [142].
Wang et al. used a protective PDA layer over Fe3O4 as a template
for MoS2 nanoflowers. The as-prepared Fe3O4-PDA-MoS2 compos-
ite combined the high surface area of MoS2 with magnetic sepa-
ration by magnetite. The nanospheres showed an adsorption
capacity of 508.9 mg/g for Pb(II) at 25ᵒC [143].
PAMAM was also involved in building supramolecular adsor-
bents for organics removal. Developing a supramolecular adsorbent
involves the non-covalent incorporation of small molecules. For
instance, Poly (methyl vinyl ether
alt
maleic anhydride) was
crosslinked with PAMAM dendrons through maleic ring-opening
and amide bond formation. The resultant supramolecular was
used for dye removal and biomolecule delivery. The adsorbent
picked up 367.7 ± 10.8 mg/g from congo red and 310.6 ± 11.2 mg/g
from sunset yellow FCF aqueous solutions. These azo dyes include
two sulfonate groups (R
SO
3 ) that produce solid electrostatic
contacts with the adsorbent's PAMAM domain [144].
7.1.8. Reactivation
Reactivation is one of the difficulties associated with adsorbents
to remove pollutants from water. Reactivation includes reverting
the adsorbent to its pre-adsorption state to reuse it. The operational
15
Materials Today Chemistry 27 (2023) 101344
cost of the adsorbent is determined by its kinetics, capacity, and
reactivability. The use of amine-based adsorbents and the under-
standing of the adsorption mechanism enable the selection of an
optimal pH for reactivation. Adsorption of anionic pollutants, for
example, frequently occurs in an acidic environment as the poly-
mer acquires a cationic character. As a result, activating requires
changing the medium to alkaline and vice versa.
For instance, Lee et al. prepared PAMAM 2nd generation den-
drimers linked through glutaraldehyde to amino-modified porous
silica foam and fibrous nano-silica. The surfaces recovered 132.4
and 88.7 mg/g of aqueous Gd(III) at the optimum pH level of 6. The
adsorption occurred when Gd(III) and Lewis basic sites in the
dendrimer coordinated. Adsorbents were regenerated at pH ¼ 3 by
protonating the amine groups to reject Gd(III) ions [145].
Leshuk et al. described a complete cycle for the flocculation and
magnetic separation of active NPs from solution. Aqueous naph-
thenic acids were combined with TiO2 mud from industrial water
samples. TiO2 was photoactivated using UV light to degrade organic
pollutants. The PDADMAC loaded on the surface of the magnetic
silica particles (Fe3O4@SiO2) in a core-shell arrangement was
employed to flocculate the TiO2 particles. After magnetic separation
of the flocs, the treated water was removed. The TiO2 NPs were
released into the acidic medium, and the bare particles (Fe3O4@-
SiO2@PDADMAC) were magnetically separated. Additionally, the
cycle was confirmed for a range of active NP suspensions, including
those containing Au, Ag, Pd, and Pt [146].
7.2. Coagulation/flocculation
Coagulation, flocculation, and sedimentation are integrated
physicochemical processes used to remove suspended solids from
water. Coagulation involves the destabilization of the colloidal
particles followed by flocculation. The destabilized particles tend to
get close enough to make contact and form progressively larger
agglomerations (Flocs). Cationic PELs are the most frequently
applied flocculants to reduce turbidity and suspended solids. PELs
might be employed as primary coagulants for stable particles or
just flocculant aid when they are added to an unstable environment
[147]. Table 3 shows illustrative examples of ARPs as coagulation/
flocculation agents. Several actions could carry out the suspension
destabilization: charge neutralization, sweep flocculation, inter-
particle bridging, or electrostatic patch mechanisms, Scheme 16.
7.2.1. Charge neutralization
Charge neutralization could be achieved by adding low Mwt
soluble ARPs. The electrostatic attraction occurs between the
cationic amine sites and the negatively charged suspended parti-
cles. A single particle can use one or more polymer chains to reach
the isoelectric point. The conformation of the polymer on the
particle surface could lead to the formation of flocs. Moreover, the
charge loss allows flocs to come close and form hydrogen bonds,
ensuring flocculation.
Zhang et al. grafted hyperbranched PEI to cellulose via the 2,3-
dialdehyde intermediate step. The resulting flocculant exhibited a
highly hyperbranched molecular structure with abundant amino
and hydroxyl groups. The flocculation performance of the sample
was evaluated by kaolin suspension (500 mg/L) before being
applied to machinery and silk dyeing wastewater. The sample of
2.4 mg/L with an amino content of 3.97 mmol/g reduced the
turbidity of kaolin suspension from 490 NTU to 4 NTU at pH 7.0 in
30 min. The charge neutralization mechanism was dominant in the
system, where zero surface potential was observed with optimum
flocculation conditions. Moreover, further increased dose resulted
in a floc size decrease due to the dissonance between charged flocs
as well as increased residual turbidity [158].
 M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay Materials Today Chemistry 27 (2023) 101344

Dendritic nanotechnology is an exciting new technique for

[148]
[148]
[149]
[150]

[151]
[152]
[153]
[154]
[155]
[156]

[157]
eliminating natural organic matter (NOM) produced by breaking
Ref.

down animal and plant wastes. Their large surface area, superior
water solubility, interior cavities, surface functionality, and

neutral
biocompatibility make them ideal for environmental applications.

5.5e6
Bhattacharya et al. efficiently removed dissolved humic acid from
8.1
8.1
6.5

9.5
pH

>7

e
8

2
water using 5th generation PAMAM dendrimers. The removal
relied on electrostatic interactions between cationic dendrimers
Temp. ( C)

and anionic humic acid at neutral pH. After charge neutralization

22 ± 2

occurred, a rapid aggregation was raised due to hydrogen bonding

15.2
15.2

25
between the neutralized complexes. Hence, micron-sized aggre-
e

e
e
e
e
e

e
gates began to precipitate [151]. Adding more generations does not
always improve the flocculation process, as the increased molecule
Initial pollutant

size competes with the effective ratio of amine groups per unit
mass [159].
7.81 NTU
7.81 NTU

88.7 NTU

100 mg/l
100 mg/l
3.5 mg/l

0.1 mg/l
50 mg/l
5 mg/l
20 g/l
dose

7.2.2. Sweep flocculation

e

Sweeping flocculation is widely used in the traditional process,

in which large flocs are formed from the coagulant itself in large
Coagulant
aid dose

doses. Hence, polymer flocs start a non-selective electrostatic ag-

(mg/l)

0.14

gregation of colloidal-sized particles over the flocs. Furthermore,

40

20
e

e
e

e
e

e
e
e

soluble pollutants might be adsorbed onto the polymer flocs and

removed from the water [160,161].
dose (mg/l)
Coagulant

Arulmathi et al. evaluated the performance of synthetic PANi

Primary

coagulant for color, chemical oxygen demand (COD), and turbidity

4000
1600

33.3

reduction in the spinning and weaving industry's wastewater. PANi

0.2

2.4

6.5
50

10
1

4
3

showed 94.38% color removal, 91.45% COD reduction, an 89.36%

lower turbidity level at pH ¼ 8, a coagulant dose of 1.6 g/L, and a
Time (min)
Conditions

contact time of 35 min. The authors did not attempt to explain the
color and COD removal mechanisms. However, they suggested that
1440
760

PANi went through the sweep-floc formation mechanism when

45
45

35

10
47

30
e

discussing turbidity. The positively charged PANi was electrostati-

cally attached to negatively charged colloidal particles at a neutral
pH level [150].
89.36 (turbidity)

PDADMAC was the first approved polymer for potable water

Efficiency (%)

94.38 (color)
91.45 (COD)

treatment by the U.S. Food and Drug Administration [162]. PDAD-

Removal

MAC is an effective flocculant for removing particulate matter from

99.3
82.5
>40

>99

water due to its solubility, biodegradability, high charge density,

100
100

~90
16
97

90

90
90
e

acceptable Mwt, and non-toxicity. PDADMAC is now available

commercially, stand-alone, blended, or copolymerized with other
Tetracycline contaminated water
Humic acid contaminated water

Humic acid contaminated water

polymers. Hou et al. prepared a PDADMAC series with different

Acid blue contaminated water

charge densities per unit Mwt (0.17  10
5 e 7.12  10
5 mmol/g),
Water under investigation

i.e., the capacity of the quaternized amine group. The samples were
Mn contaminated water

dissolved at a mass ratio of 2% in a poly ferric sulfate solution. The

flocculant as prepared was tested against heavy metal anions VO

Keddara raw water
Keddara raw water

Textile wastewater

3,
kaolin suspension

3

3
MoO2
2

Acid Green 25

4 , WO4 , AsO4 , and FeðCNÞ6 . The removal increased with

Direct Red 23
Kaolinite clay

Direct red 80
Illustrative examples of ARPs as coagulation/flocculation agents.

Acid Blue 7

increasing degrees of charge densities and decreasing valency of

the heavy metal. Sweep flocculation and charge neutralization
were the dominant mechanisms [163].

7.2.3. Interparticle bridging

Coagulant aid

PAMAM (G4)

The Interparticle bridging mechanism is predominant with high

Al(III) ions

Mwt ARPs. The chain tends to unfold due to the repulsion between
its surface charges. This formation and the high polymer charge
SDS
CS
e

e
e

e
e

e
e
e

density allow the cationic amine sites on the same chain to attract
numerous charged particles. After saturation, the chains fold back,
poly-aluminum chloride

forming a bridge between the charged particles.

Wang et al. synthesized amino-functionalized Fe3O4 NPs modi-
PEI (MW 100,000)
Aluminum sulfate

fied PAMAM dendrimer (Fe3O4@Gn-PAMAM, n ¼ 0, 1, 2, 3) as a

flocculant harvester for Chlorella sp. HQ algal cells. The high posi-
PAMAM (G5)
PAMAM (G3)
ε-polylysine

tivity PAMAM branches improved the capture of algal cells and NPs
Coagulant
Primary

rather than micro-AAs. Low pH values favored the adsorption be-

Table 3

PANi

PAM

tween algal cells and (Fe3O4@Gn-PAMAM, n ¼ 0, 1, 2), which was

PEI

PPI
CS

linked to the protonation of the amine groups over the NPs' surface.
16
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
Scheme 16. Illustration of ARP coagulation/flocculation mechanisms.
However, the high harvesting efficiency of Fe3O4@G3-PAMAM could
be maintained throughout a broad pH range owing to its highly
branching structure. The magnetic particles surrounded by the 3rd
generation dendrites (Fe3O4@G3-PAMAM) showed a high uptake
capacity of 16.1 g/g for Chlorella sp. HQ using 80 mg/L at pH 8. Large
positive active groups generally facilitated the adsorption and
bridging of negatively charged algal cells. Expendable flocs could also
be regenerated with a strong base and ultrasonication [164].
Razali et al. investigated several Mwts of PDADMAC between
8.5  104 and 15.7  104 g/mol in paper and pulp mill wastewater
treatment. The larger Mwt PEL enhanced coagulation and floccu-
lation since the longer chains form rings and tails, supporting the
bridging mechanism. Also, PDADMAC decreased the zeta-potential
magnitude, i.e., the repulsive forces between particles were
reduced, increasing the probability of the floc formation [165].
Mehta et al. synthesized polyvinyl pyrrolidone (PVP) grafted
with diallyldimethylammonium chloride (PVP-g-DADMAC) for
flocculation purposes. Dissolved PVP was mixed with the appro-
priate amount of DADMAC and ceric ammonium nitrate as a cata-
lytic. Microwave radiation (800 W) initiated the free radical
polymerization and subsequent grafting processes over the PVP
backbone. The polymer with 51 ± 2.55% grafting showed floccula-
tion efficiency of 94.6, 84.5, 82.1, 56.2, and 73.4% for 1% coal-fine
suspension, 0.25% multi-walled CNT (MWCNT) suspension, 0.25%
kaolin suspension, municipal wastewater, and river water, respec-
tively. The bridging mechanism was more conceivable in floccula-
tion with the grafted polymer. The grafting increased both the
gyration radius and hydrodynamic volume. Moreover, a consider-
able load decrease in river water and municipal wastewater was
observed for primary water quality parameters such as turbidity,
BOD, COD, TDS, TSS, total Fe, and total Cr [166].
17
Materials Today Chemistry 27 (2023) 101344
7.2.4. Electrostatic patch mechanism
An electrostatic patch mechanism occurs when a polymer with
a high charge density and a relatively small Mwt is attracted to
negatively charged surfaces with a small density of charged sites.
Herein, the suspended particles become multipolar and attract
each other, forming flocs [167].
Soros et al. investigated the impact of Mwt, deacetylation de-
gree, and functional groups on the flocculation of kaolinite and
bentonite suspensions in drinking water. CS with different Mwts
within the range of 5  103 to 1  106 Da were evaluated. The
polymer was employed at an Mwt of 50  103 Da, representing the
Mwt threshold, but with varying degrees of deacetylation from 70%
to 95%. A high deacetylation degree leads to a higher charge density
with different conformations. A low dosage of CS (1e3 mg/L,
MW > 5  103or deacetylation degree >70%) resulted in residual
turbidity <5 NTU of kaolinite and bentonite. The electrostatic patch
model better explained most of the coagulation behavior: (1) the
lack of performance of low MW CS; (2) higher deacetylation degree
CS did not perform better despite having more charge density; and
(3) performance of higher MW CS did not exceed the lower MW
products between 50  103 and 1  106 Da [168]. It is worth noting
that ε
polylysine was also tested as an alternative eco-friendly
coagulant for cohesive clay suspensions. The polymer showed su-
perior performance over the competitor CS [149].
7.3. Photocatalysis
Photocatalysis plays an essential role in exploiting renewable
energy by converting light radiation into chemical energy. One of the
most critical uses of photocatalysis with ultravioletevisible (UV-VIS)
light is to break down harmful aqueous compounds into less
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay Materials Today Chemistry 27 (2023) 101344

Table 4
Illustrative examples of photocatalysts nanomaterials based on TiO2 and ARPs.

Photocatalyst Light source Pollutant Efficiency (%) Optimum Condition Ref.

Time (min) Photocatalyst dose (g/l) Pollutant dose (mg/l) Temp. (ᵒC) pH

TiO2/CS Visible light Rhodamine B 65 180 0.3 4.98 e 3 [170]

TiO2/CS Visible light Congo red 57 180 0.3 4 e 11 [170]
TiO2/L-tyrosine Visible light Methylene blue >70% 100 0.4 3.19 e e [171]
TiO2/PDA Ultravioletevisible Rhodamine B 99.28 90 1 10 R.T e [172]
TiO2/PDA Visible light Rhodamine B 77.40 90 1 10 R.T e [172]
TiO2/PANi Visible light Methylene blue 99 360 1.12 1.6 e e [173]
TiO2/PANi Visible light Bisphenol 96.2 120 0.8 5 e e [173]
TiO2/PPy Ultravioletevisible Methyl orange 100 20 1 500 e e [174]
TiO2/PPy Visible light Methyl orange 70 240 1 500 e e [174]
TiO2/PPy Ultravioletevisible Phenol 100 20 1 50 e e [174]
TiO2/PPy Visible light Phenol 55 240 1 50 e e [174]
TiO2/PAM Ultraviolet Orange II 100 110 0.5 30 25 9.3 [175]

mischievous compounds or natural elements. Photocatalysts are
mostly semiconductors, where they absorb light energy, allowing the
transfer of negative electrons to the conduction band (CB), leaving
behind the positively charged holes in the valance band (VB).
Elevated electrons produce superoxide anion radicals ( O
2 ) by re-
action with oxygen, while holes produce active hydroxyl radicals
( OH) by reaction with water or OH
, Eqs. 2e11. Active radicals target
organic pollutants through an oxidative degradation reaction [169].
Photocatalyst þ hn/hþ þ e

hþ þ H2 O/   OH þ Hþ
hþ þ OH
/ OH
hþ þ pollutant/ðpollutantÞþ
e
þ O2 / O

2 (6)
:
O
þ 
2 þ H / OOH
2 OOH /O2 þ H2 O2
H2 O2 þ  O


2 / OH þ OH þ O2
H2 O2 þ hv/2  O H

oxidation, (2) spherical nanostructures (40 nm) through chemical
pollutant þ 
OH ; hþ ;  OOH or  O

2 /degradation Product
Table 4 shows illustrative examples of photocatalysts nano-
materials based on titanium dioxide (TiO2) and ARPs. Although not
many ARPs possess a photocatalytic activity, they might also play
other roles, including shifting adsorption to the VIS region,
pollutant attractant, and protective coating. The amino groups on
the polymer provide anchoring sites for photocatalytic materials.
The repulsion between the positive chains carrying these photo-
catalysts prevents aggregation and increases photo-contact. The
amine groups often act as absorption sites to increase the con-
centration of pollutants near the photocatalyst. The nitrogen of the
amino group might also contribute to heterojunctions that enhance
the charge separation and shift the photo-response to the VIS light
region.
7.3.1. Intrinsic photocatalytic activity
Some ARPs with organic backbones might show photocatalysis
by themselves, e.g., PANi and PPy [176,177]. Contrastly, PPD has
ortho, meta, and para isomers, only PoPD-based copolymers and
nanocomposites contribute to photocatalysis applications [178].
Few studies have been conducted combining other forms (PmPD
and PpPD) with photocatalytic materials, casting doubt on their
ability to enhance photocatalytic performance. Further criticism
can be levelled at its capacity to scavenge the radicals responsible
(2) for degradation [179].
Taymaz et al. examined, for the first time, the catalytic activity of
PANi itself and deprotonated PANi (DPANi) in the degradation of
(3) two dyes. PANi was synthesized by polymerizing ANi in acetonitrile
by chemical oxidation with periodic acid. Furthermore, DPANi was
produced by adding a solution of tetrabutylammonium hydroxide
(4)
to PANi colloidal to achieve a thorough deprotonation process.
Under UV light irradiation, both PANi and DPANi were able to show
(5) excellent photocatalytic activity. They completely degraded MB and
malachite green dyes in the presence of DPANi after 60 and 75 min
and after 45 min for both dyes when using PANi. The presence of
the hetero nitrogen of amine and imine groups in addition to the p-
conjugated network in PANi allows the electronic transitions
(7) responsible for photocatalytic activity. The bandgap for PANi and
DPANi was calculated as 4.43 eV and 5.06 eV, respectively. Although
the DPANi photocatalytic reaction was slower than PANi, it is ex-
(8) pected to be more practical at degrading pollutants due to its ability
to absorb sunlight [177].
(9) Curiously, the number of experiments in which plain PPy was
used for photocatalysis has been nil until recently. Lately, Yuan et al.
revived the subject through a comparative study of several polymer
(10) forms under different synthesis conditions. They reported three
PPy nanostructures: (1) bulky PPy through common chemical
oxidation in the presence of swollen hexagonal mesophases tem-
(11) plates, and (3) nanoballs (400 nm) by direct gamma irradiation
polymerization. All the resultant nanostructures were used for
phenol and MO photodegradation. The spherical nanostructures
exhibited the highest photodegradation under UV light illumina-
tion. At the same time, the nanoballs showed superiority under VIS
light, with no notable photoactivity for the bulky PPy. The result
was attributed to (1) more defects in the bulky polymer that
encouraged e-h recombination, and (2) conductivity increased with
the decreased surface area [176].
7.3.2. Red shifting
Chemical bonding and related charge transfer at the interface
between the photocatalyst and ARP support are anticipated to be
exploited to fine-tune the electrical and chemical features of the
18
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
active sites. For example, TiO2 is a frequently used photocatalyst for
pollutant degradation. Still, its activity is limited by absorption in
the UV range due to the wide bandgap, and photo-generated
electron-hole pairs undergo fast recombination. Shifting the ab-
sorption to the VIS light area allows the exploitation of the sun's
rays to activate the photocatalyst [180].
Nonmetal and metal components have been employed to tune
the electronic structure of TiO2 and boost its photocatalytic activity
in the VIS light region. A modified sol-gel approach was used to
create photocatalysts employing amine-terminated PAMAM den-
drimer (0th generation) as a template and source of nitrogen in N, Pt
co-doped TiO2. Within the TiO2 energy bands, N established an
inner band closer to the valence band, while Pt established another
band closer to the CB. The resultant sol-gel showed a redshift in the
adsorption over plain TiO2 [181,182].
Other photoactive materials exhibited the same gap-contracting
effect upon functionalization with PAMAM dendrimer. Mousavi
et al. immobilized CeO2-NPs onto a nanofiber mat made from
pullulan, poly (vinyl alcohol), and poly (acrylic acid) blend. Then,
CeO2-NPs were functionalized with (3-Glycidyloxypropyl)trime-
thoxysilane as a linker with the 3rd generation PAMAM dendrimer.
The modified CeO2-NPs showed a reduced bandgap of 2.91 eV
compared with 3.11 eV for pristine CeO2-NPs. The final structure
demonstrated triplicate reactivity toward azorubine and phenol
photodegradation [183].
Saad et al. synthesized two CS-based composites, CS/ZnO and
CS/CeeZnO, under 900 W of microwave irradiation. Morphological
investigation showed ZnO and Ce-doped ZnO as unique nanoflower
petals surrounded by CS leaves. The bandgaps of ZnO, CS/ZnO, and
CS/CeeZnO were 3.3, 2.85, and 2.5 eV, respectively. The synthetic
composites were applied to the photocatalytic degradation of
malachite green dye under a VIS light source. Over the immaculate
ZnO, the synthetic CS/ZnO and CS/CeeZnO composites boosted the
degradation of malachite green by 54% and 87%, respectively. After
five photocatalytic breakdown cycles, the synthetic composites
remained stable and reusable [184].
7.3.3. Heterojunction formation and photo-corrosion inhibition
Semiconductor photocatalysts are a cost-effective and environ-
mentally friendly method of removing organic pollutants and bac-
teria from water. However, the rapid recombination of optical charge
carriers and photo-corrosion limit the efficiency of semiconductor
photocatalysts [185]. Coupling conductive materials with photo-
catalysts to form heterojunction photocatalysts allows the transfer of
photo-generated charge carriers to/from conductive materials and
effectively hinders electron-hole pair recombination [186]. There-
fore, heterojunction formation is expected between conducting ARP
and photoactive semiconductors [187,188]. Moreover, hybridization
with conductive polymers inhibits the photo-corrosion of the
semiconductor-based photocatalysts by consuming the charges
responsible for the instability [185].
Sivakumar and colleagues employed LaVO4/PoPD and BiVO4/
PoPD nanocomposites for photocatalytic degradation of MB dye
and textile effluents. The degradation of MB reached 70.4% by
LaVO4/PoPD and 96.3% by BiVO4/PoPD after 120 min of VIS light
irradiation. Moreover, textile effluents were degraded by these
two composites at a rate of 97% and 94%, respectively. The sche-
matic structure of the composite energy levels is shown in
Scheme 17. Upon VIS light irradiation, electrons were excited
from the highest occupied molecular orbital (HOMO) to the
lowest unoccupied molecular orbital (LUMO) of PoPD before be-
ing transferred to the CB of MVO4, leaving holes behind. Also,
electrons migrated from the VB of MVO4 to the HOMO of PoPD,
leaving holes in the VB of MVO4. These electrons and holes were
absorbed by oxygen and water molecules on the surface of MVO4
19
Materials Today Chemistry 27 (2023) 101344
to produce superoxide and hydroxyl radicals responsible for dye
degradation [189].
Mittal et al. developed a MoSe2-PPy photocatalyst using a two-
step approach, including the hydrothermal production of MoSe2
nanosheets followed by the in-situ formation of the PPy compo-
nent. Induced photocatalytic with VIS light was investigated to
degrade the cationic Rhodamine B and anionic congo red dyes. The
as-prepared composite effectively separates photo-generated
charge carriers, thereby improving photocatalytic activity. For de-
tails, when exposed to VIS light, electrons from the valence band of
MoSe2 and PPy are excited into the CB, leaving holes behind. Photo-
generated electrons could easily be gathered into the CB of MoSe2.
Following that, electrons in the MoSe2 CB might combine with
dissolved oxygen to create superoxide anion radicals, which could
oxidize organic dyes to non-toxic products. Meanwhile, PPy's
valence band holes might directly or indirectly destroy organic dyes
by forming hydroxyl radicals. Creating this type II heterojunction is
responsible for separating charge carriers and enhancing photo-
catalytic activity [190].
The accumulation of excess photo-induced electrons/holes on
the semiconductor surface might cause photo dissolution. For
instance, cadmium sulfide (CdS) upon illumination, electrons and
holes are generated from the CB and VB, respectively. Photoex-
cited electrons are smoothly transferred to the surface, while
holes could be enriched on the outer surface, causing photoelec-
tric corrosion whether in the presence, Eqs.12e15, and the
absence of oxygen Eq. (16) [185]. Yang et al. developed a stable and
regeneratable nanosized CdS-based catalyst for VIS light-induced
photocatalytic degradation of Eosin B dye and phenolic com-
pounds. Nanosized CdS first confined in hexagonal mesoporous
silica before adding a PDADMAC PEL protection layer. Without the
PDADMAC coating, the photocatalyst ceased to be active in the
third round, but the coated photocatalyst completed over 22 cy-
cles of organic pollutant removal. Moreover, the regeneration of
catalysts was accomplished by resulfurizing the exhausted cata-
lyst powder with a stream of H2S. After regeneration, the catalyst
showed the same activity as the new catalyst for six regenerations
cycles. The PEL layer resisted cadmium leakage as it prevented the
photo-corrosion of CdS by a retrograde process involving residual
photoelectrons [191].
CdS þ hn/hþ þ e
(12)
CdS þ 4hþ þ 2H2 O þ O2 /Cd2þ þ SO2

4 þ 4H
þ
(13)
O2 þ 4e
þ 4Hþ /2OH
(14)
The overall reaction : CdS þ 2O2 /Cd2þ þ SO2

4 (15)
CdS þ 2hþ /Cd2þ þ S (16)
Ma et al. enhanced the stability and photocatalytic activity of
Ag3PO4 by using PANi and waste tobacco stem biochar. Plain
Ag3PO4 has difficulties in practical application because of its
intense photo-corrosion, Eq. (16). The coating of PANi reduced the
water solubility and self-reduction of Ag3PO4. Biochar and PANi
enhanced the charge separation by capturing electrons and holes.
Moreover, their synergistic effects reduced the particle size,
enhanced adsorption, and improved light utilization. Holes were
the main active species during the photocatalytic reaction. Triclo-
san was degraded efficiently by the optimal photocatalyst (1%T-
Biochar/Ag3PO4/1% PANi) with an 85.21% removal rate in 10 min.
Furthermore, the apparent rate constant was 2.38 times that of
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
Scheme 17. Photoproduction of superoxide anion and active hydroxyl radicals through type II heterojunction over PoPD/MVO4 nanocomposite. (Redrawn with modification from
Ref. [189]).
plain Ag3PO4. The hybrid was more durable than plain Ag3PO4
during three cycles [192].
Agþ þ e
/Ag0
7.3.4. Dispersity
The photocatalytic efficacy could be increased by a trace amount
of monocharged polymer that prevents the active NPs from ag-
gregation due to electrostatic repulsion. Krehula et al. synthesized
PPy/TiO2 nanocomposites with photocatalytic activity under VIS
light to degrade reactive red 45 azo dye. The pH level of 6.6 was
optimal for the photocatalytic degradation reaction. The removal
efficiency was 96% and 98% for TiO2 and PPy/TiO2, respectively, but
the degradation rate was enhanced. The small fraction of the PPy
immobilized onto TiO2 prevented the latter aggregation, more VIS
light photon utilization, and more contact with pollutant molecules
[193].
However, the coating thickness is an important and influential
factor and should be optimized. Mao et al. studied the effect of TiO2/
PDA-coating of different thicknesses on developing the photo-
catalytic performance on the degradation of Rhodamine B from an
aqueous solution. Initially, the encapsulation showed superior
support for the aforementioned catalytic performance due to the
increased light absorption capacity. However, increasing the layer
thickness above 1 nm leads to a decline in performance due to
charge transfer [194].
Jung et al. functionalized TiO2 with successive generations of
PAMAM magnetic dendrimers. The surface amine groups promoted
the water dispersion, and the magnetic character enabled the facile
separation. The combination was used for aqueous MO photo-
degradation. The reaction rate increased as the PAMAM generation
around TiO2 NPs increased from 0 to 3. The most significant
Materials Today Chemistry 27 (2023) 101344
increase was observed between the 1st and 2nd generations.
However, the use of higher generations was accompanied by a
higher loss of photocatalytic activity [195].
(16)
7.3.5. Pollutant attractant
Hou et al. fabricated PDA-coated TiO2 nanofibers via an elec-
trospinning process and subsequent treatment with an alkaline DA
solution. The polymerization duration tightly controlled the shell
thickness between 1.1 and 6 nm. Once the solution pH exceeded 7,
the photocatalyst's surface charge turned negative, causing an
electrostatic attraction with MB. Moreover, the PDA shell absorbed
VIS light, exciting electrons that rapidly transferred to TiO2, where
they reacted with water and oxygen to form hydroxyl and super-
oxide radicals. Herein, PDA shells served as both a photonic sensi-
tizer and a cation attractor [196].
PEI in hybrid photocatalysts could contribute to the charge
transfer mechanism. For instance, graphite carbon nitride (g-C3N4)
is a metal-free photocatalyst for drinking water disinfection.
However, its low activity denatures it. Zeng et al. showed that PEI
enabled electron transfer from its amine groups to g-C3N4, thereby
facilitating charge separation and the generation of long-lived
reactive oxygen species (O
 2 and H2O2). Meanwhile, the posi-
tively charged PEI might electrostatically attract negatively charged
bacteria cells to the photocatalyst surface. Under simulated sun
irradiation, the PEI/g-C3N4 combination efficiently inactivated the
Escherichia coli by 6.2 logs in 45 min and the Enterococcus faecalis by
4.2 logs in 60 min with no discernible adverse humic acid effect on
the process [197].
7.3.6. Template material
ARPs are also used as a template to control the morphology of
photocatalysts, particularly dendrimers and branched structures.
The inner nanocavities are used as hosts that prevent aggregation,
20
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
obtain a narrow distribution of stable NPs, and increase surface
area. Zhao et al. used PAMH as templates for constructing micro-
flowers of Ag/AgCl/BiOCl-X photocatalysts with the solvothermal
method, where X indirectly represents the polymer content. The
formation of Ag particles results from two processes: the AgNO3
reduction and the surface AgCl reduction after VIS light exposure.
The degradation of Rhodamine B and tetracycline under VIS light
irradiation (l > 400 nm) was used to assess the photocatalytic ac-
tivity of the as-fabricated composites [198].
Kim et al. coated electrospun polyurethane nanofibers with PDA
via the dip-coating method. The resulting nanofibrous was
immersed in an aqueous ZnO NP solution to seed the metal oxide
particles on its surface. Later, ZnO nanorods were grown on the
ZnO-seeds via a hydrothermal process. The PDA catechol group
worked as an electron trap, reducing electron-hole pair recombi-
nation and increasing photocatalytic effectiveness [199].
BiVO4 is a VIS light active n-type semiconductor with three
forms: tetragonal scheelite, tetragonal zircon, and monoclinic
scheelite. The monoclinic phase was recommended for VIS light
applications due to its narrow bandgap of 2.4 eV. Mahlalela et al.
synthesized {010} monoclinic BiVO4 facets with plate-like
morphology with the addition of 0.5 M NaCl and 0.15 mM hyper-
branched PEI for the decomposition of aqueous atrazine. The sur-
face area was increased by 88% from 0.7 m2/g for 0.5NaCleBiVO4 to
1.32 m2/g for 0.15PEIe0.5NaCleBiVO4. However, after forming p-n
junctions in 0.15PEIe0.5NaCleBiVO4eBi2O3, the bandgap was
increased to 2.43 eV. Hence, the decomposition of atrazine in
wastewater remained higher in 0.5NaCleBiVO4eBi2O3, which
warrants further study [200,201].
7.3.7. Coupling multiple active sites
Photo-generated carriers might be transported in many phases
through the induction mechanism to separate electrons and holes
throughout the ternary catalytic reaction process, extending pho-
tocatalytic activity beyond the binary catalytic system. Li et al.
utilized a PDA bridge to crosslink ZnAl-layered double hydroxide
(ZnAl-LDH) nanosheets with g-C3N4 to create a VIS light Z-scheme
heterojunction photocatalyst, Scheme 18a. Under VIS light, elec-
trons from each of the VB of the active materials were excited to
their respective CB. The photo-induced electrons of CB on g-C3N4
will be transferred to the VB of ZnAl-LDH via the PDA p-p* tran-
sition to provide additional electron transfer channels. The holes in
VB of g-C3N4 and electrons on the CB of ZnAl-LDH, as well as the
abundant electrons on the PDA, contributed to radical formation.
While all active species have developed, their impact on the
degradation reaction differs with the order (hþ > OH > O
 2 ) [202].
The PDA generally does not show photocatalytic activity by it-
self. Therefore, conductive ARP with photoactivity might contribute
to other effective ternary heterostructures. Balakumar et al. syn-
thesized ternary porous g-C3N4/PPy/montmorillonite (MMt) via an
in situ oxidative polymerization method. The photocatalytic per-
formance towards the mineralization of metronidazole antibiotic
under VIS light was studied. The g-C3N4/PPy/MMt(10%) nano-
composite exhibited the best performance than the g-C3N4/PPy/
MMt(5%, 15%, 20%), g-C3N4/PPy, plain g-C3N4/PPy. This enhanced
photocatalytic capability has been linked to synergistic interactions
between constituents, Scheme 18c. During VIS light irradiation, the
VB of MMt and g-C3N4 captured the photo-generated electrons of
PPy. Affluent ( O
2 ) radicals were produced by the electrons in the
CB of g-C3N4 and MMt, whereas water produced ( OH) radicals by
the holes in the VB. The holes in MMt's VB and PPy's HOMO were
directly implicated in metronidazole degradation. After five pho-
tocatalytic cycles, the photocatalyst was still very effective and
stable [203].
21
Materials Today Chemistry 27 (2023) 101344
Faisal et al. synthesized a ternary photocatalyst using ZnTiO3
nanostructures doped with PANi and Ag NPs via a modified sol-gel
method followed by an ultrasonication approach. Under VIS light,
the as-prepared Ag/PANi/ZnTiO3 nanocomposites were effectively
used to photodegrade MB and imidacloprid aqueous molecules.
The ternary photocatalyst composed of Ag (1%)/PANi(10%)/ZnTiO3
showed exceptional efficiency, removing 95.6% of the target MB
molecule and achieving a degradation rate 1.85 times that of
undoped ZnTiO3. With VIS light, conducting polymer PANi feeds
electrons to the CB of ZnTiO3. Hence, surface plasmon resonance
occurs, causing the equilibrated Fermi level of Ag to flow rapidly
into the ZnTiO3 conduction band, Scheme 18b [204].
7.4. Filtration membranes
Microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and
reverse osmosis (RO) are used to describe different types of filtra-
tion membranes depending on the pore size used to reject various
contaminants. The primary contrast between reverse and forward
osmosis (FO) is how water is driven through the membrane. In RO,
hydraulic pressure forces water through the membrane, whereas
natural osmotic pressure is dominant in FO. The fundamental
membrane characteristics are the water contact angle (WCA), water
flux, fouling tendency, surface charge, roughness, and pore size.
Porous MF and UF membranes are manufactured by controlled
deposition of membrane components in layers or hollow fibers in a
process known as phase inversion. MF and UF membranes are
usually applied in cross-flow or dead-end flow configurations to
remove suspended particles, large organic compounds, bacteria,
and viruses. The composite NF and RO membrane is usually made
by condensation polymerization at the interface between the
aqueous and organic phases. NF and RO are applied cross-flow
configurations for salt rejection and small organic compounds
[205].
7.4.1. Hydrophilicity
Membrane fouling is defined as a decrease in flux caused by the
accumulation of contaminants on the surface, which causes pore-
clogging. Contaminated materials include inorganic, organic, and
biological materials that might permanently or temporarily
obstruct flux depending on their interaction with the membrane
surface [206]. The deposition of ARP with abundant amine groups
onto the membrane surface increases the hydrophilicity of the
membrane. A hydrophilic membrane is preferred because of the
low fouling that arises from the ability of the amino group to form a
hydration layer that weakens the adhesion of the hydrophobic
foulants.
The WCA indicates a membrane's hydrophilicity and wetting
behavior; as the WCA decreases, the hydrophilicity increases.
However, the WCA is also influenced by the surface morphology of
the membrane, such as roughness and pore size [207]. For instance,
the PDA-intercalated thin-film nanocomposite polysulfone (PSF)
membrane showed a diminishing WCA from 92.6 ± 5.3 to

35.3 ± 2.6 with the PDA coating time from 0 to 24 h due to the PDA
hydrophilic amine and catechol groups [208].
7.4.2. Pores reforming
Numerous approaches for the modulation of membranes have
been devised, including surface and bulk modification. Surface
grafting and coating were often utilized to increase the membrane
fouling resistance by providing a hydrophilic character [206].
However, these approaches alter just the membrane's outer surface
and often result in a decrease in the size of the pores as a result of
polymer deposition. Controlling the pores' size through polymer
deposition contributes to the membrane's selectivity. Chajanovsky
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
Scheme 18. (a) Z-scheme of ZnAl-LDH/PDA/g-C3N4 photocatalyst mechanism under visible light; (b) conductive type heterojunction of Ag/PANi/ZnTiO3 photocatalyst; (c) sensi-
tization mechanism of g-C3N4/PPy/MMt under visible light irradiation. (Redrawn with modification from Ref. [202e204]).
et al. prepared a buckypaper membrane by in-situ reverse emulsion
polymerization in ethanol under ANi sonication in the presence of
CNTs. The permeability of the PANi-grafted CNT was much less than
the CNT reference. However, the declined water permeability
shifted the membrane filtration to the UF region with an average
pore size of ~119 ± 28.3 nm. The 2.56 mm thick films showed high
salt removal properties at low-pressure drops, making them
promising in low-energy areas [209].
On the other hand, the bulk modification includes blending the
membrane substrate with hydrophilic ARP additives with a bene-
ficial change in hydrophilicity and pore size. Díez et al. developed
polyvinylchloride (PVC) UF membranes with a hyperbranched
PAMAM (Helux-3316) through a nucleophilic chlorine substitution
in the casting solution. The non-solvent induced phase inversion
method was used. The casting solution had a 15%w/w PVC base
material, pore-forming PVP (0e5%w/w), N, N-dimethylacetamide,
and Helux-331 (0, 0.8, 1.6%w/w). Amino groups boosted the plain
PVC membrane hydrophilicity as the WCA decreased from
78.4 ± 2.7 to 69.3 ± 1.9 with 1.6%w/w Helux-331. The finger-like
pore diameter increased from 35.5 ± 1.0 nm in the bare PVC
membrane to 47.1 ± 0.6 nm in the PVC/PVP/Helux-331, as did the
permeability, which increased from 89.5 ± 2.7 to 149.4 ± 0.6 L/m2.
hr.atm [210].
7.4.3. Surface roughness
The surface roughness of the modified membrane depends on
the modification polymer, method, and coverage. For example, the
surface could be rougher if polymer scraps grew on the surface
22
Materials Today Chemistry 27 (2023) 101344
instead of covering it. Chen et al. synthesized RO membranes by
grafting linear PEI with varying Mwt (0.6, 1.800, 10, and 70 K) onto
Dow Chemical's LE-400 polyamide surfaces. The WCA of the
membrane surface fell significantly from 65 to 36 as the Mwt of PEI
increased. However, as the surface got denser, the water flow across
the PEI-modified membranes was reduced from 64 to 51.50 L/m2h.
Grafting with a low-Mwt PEI might flatten the surface and reduce
the roughness. In contrast, the higher the PEI chain length, the
surface retained more roughness. The modified RO (70 K) mem-
brane demonstrated a decontamination factor of 114.23 for Cs(I)
and 3306.88 for Co(II) nuclides, which was more significant than
the decontamination factor of some commercial RO membranes
[211].
Ma et al. prepared PPD/polyacrylonitrile NF membrane by in-
situ PPD growth directly on the polyacrylonitrile substrate. The
polymerization rate varies according to the monomer, sorted in the
following declined order: pPD, AN, mPD, and oPD. Most PoPD
produced were oligomers with some water solubility. Hence, the
polyacrylonitrile substrate could not be fully covered, resulting in
higher permeance of pure water and minimal dye rejection. The
PpPD/polyacrylonitrile NF membrane had superior water per-
meance of 297 Lm
2/h/bar. Between pPD and oPD, the ANI and
mPD monomers polymerized at a moderate pace, leading to a high
polymerization degree and uniform coverage. As a result, the pro-
duced membrane exhibited low permeance to clean water but
significant dye rejection. The pure water permeance of all these
composite membranes was more than 170 Lm
2/h/bar, and the
congo red and direct red 23 rejection was more than 99% [212].
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
7.4.4. Control surface charge
From fouling vision, membranes' surfaces are often negatively
charged. It seems reasonable, given that most colloidal particles
that deposit on the membrane surface are negatively charged (e.g.,
NOMs, BSA, and NaAlg). However, efforts have been made to pro-
duce positively charged membranes. Positively charged surface
membranes act as barriers for cationic pollutants by an exclusion
mechanism (section 7.4.7). Thus, layer-by-layer (LbL) deposition,
copolymerization, and zwitterion formation might be more effec-
tive in introducing both charges while maintaining notable
performance.
Nayak et al. synthesized a series of PVDF membranes based on
the reactive nature of PDA to graft short-chain amino alkanes (EDA,
diethylene triamine (DETA), triethylene tetraamine (TETA), and
tetraethylene pentaamine (TEPA)). The surface was then reacted
with 1,3-propanesultone for zwitterion formation. After a 5 s in-
terval, the dynamic WCA drops from 107.8 ± 1.28 for PVDF to
59.3 ± 2.49 for PVDF-PDA membranes, where the lowest value was
31.58 ± 1.27 for the zwitternized PVDF-TEPA membrane. The alkyl
amine developed a more positive charge, thus shifting the iso-
electric point towards a higher pH level. Further functionalization
with 1,3-propanesultone slightly lowered the isoelectric point due
to the incorporation of negatively charged sulfonate groups. The
high BSA adsorption on the PVDF membrane with a negative zeta
potential could be owing to the surface's hydrophobicity, resulting
in strong hydrophobic-hydrophobic interaction. In contrast, the
zwitterionic membranes demonstrated a high level of anti-fouling
activity. The relative BSA solution flux data indicates that a clean
PVDF membrane reduces flow by more than 40%, whereas zwit-
terionic membranes reduce flux by only 2e3% [213]. The anti-
fouling effect due to the hydrophilicity effect often overcomes the
counter effect of the electrostatic attraction between opposite
charges. Furthermore, the fouling transformed from irreversible to
reversible [213,214].
Li et al. fabricated an NF membrane with 2.5 bilayers of poly
(styrenesulfonic acid) PSS and PAH through a layer-by-layer
deposition. The as-prepared membrane was further modified via
H2O2/CuSO4 triggered co-deposition of PDA/PEI. Subsequently, the
membrane was crosslinked with a glutaraldehyde solution. The
WCA of the plain substrate (PES) dropped from 80.0 to 20.0 in the
crosslinked composite membrane, indicating enhanced hydrophi-
licity. However, the water permeability drastically decreased from
110.0 to 13.1 Lm
2/h/bar. The PDA/PEI layer improved the anti-
fouling performance of the NF membrane. The membrane water
flux dropped slightly to 10.2 and 9.7 Lm
2/h/bar within 10 h and
50 h, respectively. The membrane rejected ~90.6%, 76.9%, 95.6%, and
40.4% of TOC, Ca2þ, Mg2þ, and Naþ feed content, respectively, which
was better than the NF membrane of Dow Chemical (FILMTEC™ NF
270) [215].
7.4.5. Biofouling resistance
Biofouling is the unplanned deposition and proliferation of
microorganisms. They might pollute water, cover and plug active
areas, host diseases, and assault the surface [216]. The cationic
amine and quaternary ammonium groups possess a disinfectant
character. The disinfectant properties arise from the positive charge
that makes them bindable to the microbes' surfaces with the
opposite charge.
Ismail et al. constructed a nanohybrid using quaternized silica
(GTMAC) and DA in a single step using mussel-inspired GO
tailoring. The UF hybrid membranes (rGO/GTMAC/PDA/PES) were
fabricated from PES (58 kDa), nanohybrid, and pore-forming
polymer (PVP, 40 kDa) through induced phase separation. The dy-
namic WCA dropped from 64.9 for the plain membrane to 22.6
after 8% modification due to functional moieties capable of
23
Materials Today Chemistry 27 (2023) 101344
retaining water (
OH;
NH
; and
NðCH3 Þþ 3 ). As a result, pure
water flow rose dramatically from 139 Lm
2/h for plain membrane
at 1 bar, reaching 270 Lm
2/h for membrane with 6 wt% loadings at
1 bar. The rejection of the 6 wt% hybrid membranes reached 98% for
BSA and was unaffected by enhanced flux. Quaternary ammonium
moieties also caused a strong antibacterial action against Escher-
ichia coli. Their positively charged surfaces attracted the negatively
charged bacteria and degraded their cell membranes [75].
Khoerunnisa et al. developed another polyethersulfone (PES)-
based UF membrane by a phase inversion method employing CS/
NH4Cl solutions. The modified membrane demonstrated bio-anti-
fouling capabilities, killing 99.2% of Staphylococcus aureus and
83.3% of Escherichia coli. The surface's hydrophilicity was also
enhanced, as the WCA dropped from 82.3 to 64.4 . Finally, the
membrane porosity rose from 49.6 to 70%, and the mechanical
strength increased from 0.57 to 8.7 MPa upon modification [217].
7.4.6. Sorption
Rather than sieving action, sorption membranes could retain
pollutants from wastewater during filtration based on their
adsorption groups and unique morphology. Kalita and others had
manufactured GO papers with different charges for use in selective
vacuum filtration of solutions of anionic and cationic dyes. The
negative charge of GO was related to the oxygen-rich functional
groups. In contrast, a PAM-functionalized GO solution with a
cationic character formed the positively charged paper. In both
cases, GO was used in conjunction with a polycarbonate film to
filter MB and MO dyes. The two-charge stacking structure suc-
ceeded in removing 99.8% and 99.5% of dyes, with maximum
adsorption of 311 and 340 mg/g for both MB and MO dye, respec-
tively. The rejection mechanisms included adsorption through
electrostatic interaction between the dye and the charged GO pa-
pers [218].
Sun et al. successfully prepared a PVAm-modified poly-
propylene cationic adsorption membrane using a two-step
approach. Free radical polymerization was carried out for the
grafted N-vinylformamide. The Amino groups were regenerated by
hydrolysis poly (N-vinylformamide). The solution of Cr(VI) ions was
allowed to flow downward through the membrane by gravity. The
maximum adsorption capacity of Cr(VI) was 208.3 mg/g at
pH ¼ 2e3 and 40  C, with a 55 wt% inoculation rate and a 70e80%
hydrolysis degree. Under acidic conditions, the protonation of
pendant amino groups increased the charge attraction for Cr(VI)
anions. At high solution pH levels, the adsorption of Cr(VI) species
on the aminated surface was most likely due to the formation of
hydrogen bonds and surface complexation. Additionally, the
fibrous membrane demonstrated good recycling properties owing
to the reversible protonation of the PVAm grafts' amine groups.
After ten adsorption-desorption cycles, 90.6% of Cr(VI) was
removed [219].
7.4.7. Ion repulsion
Negative-charged membranes frequently have difficulty reject-
ing polyvalent cations compared to monovalent ions, as the latter
take on anionic forms in solution. De
on et al. described a surface
modification of the commercial polyamide membrane (Desal GK)
by allylamine plasma polymerization. The cationic surface rejected
the positive cations, whereas the negatively charged pores led to a
high rejection of the anions. This allows for high selectivity of
divalent and monovalent ions regardless of their sign [220].
Creating an ammonia-selective FO membrane is crucial for
treating home wastewater. Nevertheless, it is complicated due to
the equivalent ammonium polarities and hydraulic radii of water.
Bao et al. tested PAMAM dendrimer to improve ammonia rejection
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
and anti-fouling properties of the thin-film composite (TFC) FO
membrane. The grafted membrane demonstrated ammonia rejec-
tion enhancement due to electrostatic repulsion [221,222].
Mahmoudian and others polymerized DADMAC in the presence
of carboxylated-MWCNT before incorporating the resultant com-
posite with different weights of 1, 3, 5, and 7 wt% into the PES
membrane matrix to separate salts, metal ions, and dyes from
water. The polymer's repeated positive increased the membrane
hydrophilicity. Hence, the WCA decreased from 87 in the plain PES
membranes to 62 in the 7% modified membrane, resulting in
increased water flow. Salts and MB dye rejection were enhanced by
increasing the modification from 1 to 5%wt owing to the size
optimization and Donnan exclusion. However, rejection deterio-
rated at higher modification ratios due to the extended pore size
and sponge structures. The charge variations of the quaternary N
were consistent with the membrane response at different pH levels
[223].
7.4.8. Polymer enhanced filtration
Only pollutants with an Mwt of 300 to 1 KDa can be removed
through UF membranes. Hence, they cannot reject most heavy
metal ions and organic pollutants. The water-soluble polymers
were suggested to assemble contaminants to relatively higher
Mwts than the Mwt cut-off (MWCO) to easily undergo UF, i.e.,
polymer enhanced UF (PEUF) [224]. MWCO is the lowest Mwt that
the membrane retains at a sufficient percentage (90e100%).
Diallo and his colleagues proposed using soluble dendrimers in
the adsorption of cations and anions before the filtration process.
The process utilises filtration processes at the micro- and ultra-
scales rather than NF and RO, which occur at high pressures
[225]. For instance, Diallo et al. proposed using 5th generation PPI
dendritic macromolecules to generate selective, high-capacity, and
recyclable ligands to recover perchlorate anions (ClO
4 ) from
aqueous solutions. The 5th generation PPI dendrimer with a ter-
minal (
NH2 ) groups and a DAB core exhibited perchlorate
adsorption equivalent to perchlorate-selective ion-exchange resins
but with faster kinetics as the equilibrium was reached in less than
1 h. Only an alkaline water solution (pH ¼ 9.0) is required to liberate
over 90% of the bound ClO
4 anions [226].
Moreover, Lin et al. also employed cetyltrimethylammonium
(CTAB) and PDADMAC for sulfate removal with the regenerated
cellulose membrane through micellar-enhanced UF (MEUF) and
PEUF. UF performance was studied at various starting sulfate
(0e20 mM) and CTAB/PDADMAC (0e100 mM) concentrations. In
dilute solutions, more than 99% sulfate retention was attained. At
high sulfate concentrations (e.g., 10 mM), a dose of 50 mM CTAB or
PDADMAC might retain around 90% of the sulfate ions. PEUF out-
performs MEUF in sulfate retention at lower polymer-to-sulfate
ratios and cleaner effluent, but with lower flux and higher fouling
tendency. However, the membrane fouling was reversible, and the
membranes could be reused [227].
Huang et al. have focused on discarding heavy metal ions from
an aqueous solution by PVAm-enhanced UF across a PES membrane
(MWCO ¼ 10 kDa). Cu(II), Fe(III), and Pb(II) gave nearly complete
rejections, while Ni(II), Mn(II), Co(II), Cd(II), and Zn(II) were much
weaker. The metal rejection in PEUF was highly correlated to metal-
amine-polymer complexes. The ascending polymer-to-metal ion
ratio increased the rejection process; however, the flux across the
membrane decreased. Crosslinking of PVAm with the sulfate anions
in the solution would cause precipitation. Hence, PVAm could be
handled as either a flocculant for high concentration metal ions or
an enhancer of UF for low concentration metal ions [228].
PDADMAC was also used to aggregate anionic MO dyes in the
PEUF process. A regenerated cellulose membrane was applied for
24
Materials Today Chemistry 27 (2023) 101344
UF with an MWCO of 10 kDa. In the PDADMAC-MO system, the
positive charge of the polycation was progressively increased at
acidic pH levels, which allowed it to attract more MO molecules.
The authors validate the polymer's reusability after four sorption-
desorption cycles [229].
7.4.9. UV resistance
In materials science, “oxidative degradation” always refers to
polymer degradation. This self-stimulating process includes the
formation of hydroperoxides as a result of hydrogen atoms' attack
by oxygen on the carbonic backbone. The stability of polymers
against oxidative degradation depends on saturation degree,
branched structure, crosslinking, and crystallization [230]. Polymer
oxidation is often accelerated by sunlight, ozone, heat, radiation,
mechanical stress, traces of transition metal ions, water, pollutants,
and microorganisms. For instance, the PDA layer was used as a UV
protective layer for the polyvinylidene difluoride (PVDF) mem-
brane. PDA's UV protective properties were ascribed to the high
abundance of catecholamine groups. The latter could capture free
radicals and inhibit the membrane's UV-induced photodegradation
[231].
7.4.10. Acid resistance
Zeng et al. created an acid-resistant NF membrane by interfacial
polymerization of 1,3,5-(tris-piperazine)-triazine on the surface of
a PSF UF membrane with TMC. The composite membrane was
equipped with a smooth and highly crosslinked poly (amide-s-
triazine-amine) skin layer with an isoelectric point near pH ¼ 3.5.
The membrane had a water permeance of approximately
8.68 Lm
2/h/bar and a salt rejection of greater than 97% for 2 g/l
divalent salt solutions at 100 psi pressure. Salts were rejected in the
order of Na2SO4 > MgSO4 > NaCl, as was typical for negatively
charged membranes. After 720 h of exposure to 0.05 M H2SO4, the
membrane blocked more than 94% of MgSO4 with no noticeable
chemical or morphological changes in the membrane skin layer
[232].
7.5. Miscellaneous roles
7.5.1. Solubility
While chitin is insoluble in numerous organic solvents, CS is
highly soluble in dilute acidic solutions below pKa. The pH signifi-
cantly affects the charged state of amino groups and the charac-
teristics of CS. These amines get protonated and positively charged
at low pH, transforming CS into a water-soluble cationic PEL. On the
other hand, as the pH increases, CS amines are deprotonated;
hence, the polymer loses its charge and becomes insoluble [233].
Moreover, the degree of CS deacetylation refers to the ratio of the
acetyl groups that were converted to amine groups during the CS-
chitin conversion. By definition, the degree of deacetylation directly
expresses the density of amine groups on the CS constituent. With
increasing the degree of deacetylation, the repulsion between the
amine charges increases. As a result, the viscosity of the polymer
decreases and the solubility increases [96].
Numerous ARPs exhibit analogous behavior owing to their
functional group dependency. Kawakita et al. exploited the solu-
bility and reduction capability of Poly (Tyr) to recover gold ions
from aqueous solutions, Scheme 19. First, the aqueous solution was
acidified with HCl (pH ¼ 1). Then, poly (Tyr) was dispersed in the
solution. Poly (Tyr) phenolic groups reduced gold ions into particles
separatable by filtration. Poly (Tyr) precipitates at pH ¼ 7 as the
amine group can no longer acquire protons. As a result, the gold ion
reduction process was based on the hydroxyl and amino groups.
Moreover, the polymer separation was based on the solubility
change as the amine group environment changed [234,235].
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
7.5.2. Demulsification
The emulsion is a two-phase system composed of two liquids
that do not mix homogeneously, one of which is dispersed in the
other phase as globules. Demulsifiers are a class of chemicals or
surfactants used to separate the two phases. Water-soluble
demulsifiers are used to destabilize oil-in-water emulsions and
vice versa [236]. Zhang et al. synthesized two PAMAM with 1,3-
propanediamine and EDA initiators for the demulsification of oil-
water emulsions. The demulsifier based on 1,3-propanediamine
has excellent performance, achieving an oil removal ratio of up to
92% after 30 min. This superior demulsification performance was
due to the synergistic effects of the hyperbranched structure and
the appropriate Mwt. Hence, the PAMAM demulsifiers showed high
interfacial activity, capable of destabilizing emulsions and floccu-
lating oil droplets to facilitate phase separation [237].
In the petroleum industry, two spaced Mwts of branched PEI
(10 k and 60 k) coupled with an anionic sodium dodecylbenzene
sulfonate surfactant (SDBS) were used to treat oily water. As the
concentration of SDBS in the medium increased, it accumulated on
the surface of the oil droplet until saturation, corresponding to the
maximum removal efficiency. The higher the cationic demand, the
lower the Mwt required for efficient flocculation of oil droplets. The
oil removal efficiencies of the PEI were equivalent to those of the
reference polymer in low concentrations of SDBS and better in
greater concentrations [238].
Soluble pEPI-DMA contains hydrophobic methyl and hydro-
philic quaternary amine groups, making it a distinct coagulation
agent. Additionally, the polymer has a controllable charge density, a
low Mw, and cost-effectiveness. Mineral salts are used to destabi-
lize the colloids in dishwasher wastewater. Cationic polymers are
examined as a potential alternative to the commercial metallic
alum salt used for this purpose. Recently, pEPI-DMA showed
excellent removal efficiency compared to alum and other cationic
polymers. At a small dose of 0.1 mg/l, the polymer removed 87% of
oil and 90% of turbidity. The removal efficiencies were increased
when the polymer was used in conjunction with the alum, but
there was a performance disturbance with samples of varying
strengths or pH levels [239].
Scheme 19. Poly (tyramine) cycle for gold recovery. (Reprinted with permission from Ref. [234]. Copyright © 2010 American Chemical Society).
25
Materials Today Chemistry 27 (2023) 101344
7.5.3. Encapsulation material
Water instability, limited sorption capacity, and selectivity are
common drawbacks of adsorbents based on metal-organic frame-
works (MOFs). Yuan et al. coated the MOF-199 core with a PANi
shell and used it for the adsorption of Cu(II) ions to eliminate these
issues. The encapsulation process aimed to protect the structure of
the MOF and provide additional adsorption sites. The isothermal
data suited the Langmuir model, and the predicted adsorption ca-
pacity was 7831.34 mg/g. The porous architecture of MOF-199 and
the complexation between Cu(II) and N atoms of PANi might have
contributed to the excellent adsorption [240].
8. Future perspectives
Following is a demo of the most important future aspects for
optimizing the utilization of ARPs in water treatment:
[1] The performance optimization of ARPs and their roles in
standalone, hybrid, and composite nanomaterials requires
determining the surface/bulk amine group densities. Despite
the variety of techniques available, surface group quantifi-
cation remains an obstacle. In most instances, only a quali-
tative identification of the surface groups was performed.
Therefore, a simple, reproducible method or protocol for
determining the amino group's density remains a challenge.
[2] There is a general trend in the scientific community toward
the use of environmentally friendly materials and green
polymers. In this context, CS and PDA have recently received
a great deal of attention. However, natural polymers such as
PDA analogs and PAAs are not given the same level of
consideration. Despite the fact that the latter has a high
amine group content and the capacity to form dendrimers.
[3] Most ARP nanomaterial synthesis is straightforward. How-
ever, more analysis and optimization for critical factors are
still required. For instance, reaction parameters and stability
issues can influence the nanomaterials' behavior, morphol-
ogies, and pollutant removal performance. In addition,
further attention is encouraged to polymers with synthesis
M.E. Elhalwagy, A.S. Elsherbiny and A.H. Gemeay
complications that limit their study and application, such as
triazine dendrimers.
[4] Creating a greater diversity of nanocomposites based on
ARPs through permutations and harmonics of dendrimers,
quaternization, and copolymerization.
9. Conclusion
The design and development of highly reactive nanomaterials
have emerged as one of the most promising strategies for water
purification and pollution control. Here, the focus is on ARPs, where
it was necessary to carefully study their behavior to determine their
roles in water treatment applications.
Adsorption e The ARPs were used to build adsorbent materials
to remove contaminants from the water. Below the zero-charge
point, the nitrogen atom acquires a cationic character, through
which it can attract anionic pollutants and vice versa. ARP quater-
nization might cause the isoelectric point to shift to a higher pH
value, prolonging the cationic behavior. Additionally, the pH-
dependent swing of the ARP surface charge was used to regen-
erate the surface. The nitrogen atom also plays a role in hydrogen
bonding and heavy metal chelation with a redox process that might
follow. ARP was synergistically used to connect multiple adsorptive
layers based on the reactivity of the amine groups.
Coagulation/Flocculation e Cationic PELs are the most often
used flocculants to decrease turbidity and suspended particles. The
diversity of ARPs in structures, compositions, solubility, and charge
density, facilitates their adaptation for different flocculation and
coagulation applications. The low-Mwt, soluble ARPs with
branched or dendritic structures could neutralize the negatively
charged suspended particles. The charge loss allows flocs to come
close and form hydrogen bonds, ensuring flocculation. Less soluble,
viscous, and high Mwt ARPs, like PANi, perform non-selective
sweep floc aggregation of colloidal-sized particles. NPs function-
alized with ARPs, as well as long-chain ARPs with high charge
densities, tend to bridge numerous charged particles. High charge
density and relatively small Mwt ARPs, e.g., CS, convert the surface
of the suspended particles into a multipolar surface able to attract
each other.
Photocatalysis e Some ARPs showed photocatalysis by them-
selves, such as PANi and PPy. Some of the others, like PmPD and
PpPD, might be obstructions. In general, the nitrogen of the amino
group might contribute to heterojunctions that enhance the charge
separation and shift the photo-response to the visible light region.
Moreover, the amino groups on the polymer provide anchoring
sites for photocatalytic materials. Hence, the repulsion between the
positive chains carrying these photocatalysts prevents aggregation
and increases photo-contact. The amine groups often act as
pollutant attractant sites to increase the concentration of pollutants
around the photocatalyst. ARPs could also be used as template
material for photocatalysts with enhanced morphological
structure.
Filtration Membranes e The hydrophilicity of the amino group
forms a hydration layer that weakens the adhesion of the hydro-
phobic foulants. The ARPs could also be used to control the size of
the pores. ARP surface deposition leads to a narrowing of the size of
the pores. On the other hand, bulk modification might lead to
different results depending on the type of polymer, substrate, ad-
ditives, and their ratios. While negative membranes support the
repelling of negative foulants, positively charged membranes act as
an exclusion barrier for cationic pollutants. Although the capacity
to reject negative pollutants decreases with the addition of ARPs,
fouling resistance rises owing to the stronger hydrophilic effect.
Moreover, the cationic amine/ammonium groups possess a disin-
fectant character. Soluble ARPs (Section 3.2) are the mainstay of the
26
Materials Today Chemistry 27 (2023) 101344
PEUF process. Finally, the presence of an ARP coating might provide
extra protection against chemicals and UV radiation.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Data availability
No data was used for the research described in the article.
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