Environmental Research 162 (2018) 173–195

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Review article

Nanoadsorbents based on conducting polymer nanocomposites with main T

focus on polyaniline and its derivatives for removal of heavy metal ions/
dyes: A review
⁎
Ehsan Nazarzadeh Zarea, , Ahmad Motaharib, Mika Sillanpääc
a
School of Chemistry, Damghan University, P.O. Box: 36716-41167, Damghan, Iran
b
Young Researchers and Elite Club, Jahrom Branch, Islamic Azad University, Jahrom 74147-85318, Iran
c
Laboratory of Green Chemistry, Lappeenranta University of Technology, Sammonkatu 12, Mikkeli 50130, Finland

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

Keywords: Water contamination by toxic heavy metal ions and dyes remains a serious public health problem for humans, so
Nanoadsorbents attention on specific methods and technologies to remove heavy metal ions and dyes from wastewaters/aqueous
Polyaniline and its derivatives solutions are desired. Numerous adsorbents have been reported for the removal of heavy metal ions/dyes from
Heavy metal ions wastewaters/aqueous solutions. Polyaniline (PANI) and its derivatives, as conducting polymers, are good ad-
Dyes
sorbents to remove various kinds of heavy metal ions and dyes from wastewaters/aqueous solutions. The na-
Adsorption
noadsorbents based on PANI and its derivatives have received much consideration, and are extensively reported
in literature. This review focuses on the PANI and its derivatives based on nanoadsorbents for water purification.
Various types of these nanoadsorbents used for the removal of heavy metal ions/dyes from wastewaters/aqueous
solutions are also briefly compared in this review.

1. Introduction
1.1. The importance of safe drinking water
Water is a vitally important compound for human life. About 60% of the
human body is water. Water is also an essential resource for producing food,
clothing, and maintaining our health and environment (Zare et al., 2016), so
access to safe drinking water is very important all over the world. The
generation of an enormous amount of harmful chemical waste from various
industries, and its improper disposal further intensifies the water crisis
(Huang et al., 2014). Pollutants can be divided into four categories: phy-
sical, chemical, biological and radiological (Bernard and Nebel, 1999).

Abbreviations: PANI, Polyaniline; As, Arsenic; Hg, Mercury; Cr, Chromium; Pb, Lead; Ni, Nickel; Cd, Cadmium; Co, Cobalt; Cu, Copper; RHS, Rice husk; WS, Walnut shell; OP, Orange
peel; SFSS, Sunflower seed shells; ES, Eggshell; SD, Sawdust; PP, Pomegranate peel; CP, Carrot pulp; SB, Soybean; CSH, Cottonseed hulls; OS, Olive Stone; FA, Fly ash; CR, Congo red; IC,
Indigo carmine; C.I., Color index; RB, Rhodamine B; AD, Azo dyes; ADAO, Azo dye acid orange; DD, Diazo dye; MB, Methylene blue; MO, Methylene orange; AO, Acid orange; NR, Neutral
red; BD, Basic dye; CNTs, Carbon nanotubes; MWCNTs, Multi walled carbon nanotubes; G, Graphene; GO, Graphene oxide; MGO, Malachite green oxalate; RBBR, Remazol brilliant blue
R; CD, Cationic dyes; MV, Methyl violet; RB, Rhodamine B; OG, Orange G; RR, Reactive red; RB, Reactive blue; AB, Acid black; COD, Chemical oxygen demand; EY, Eosin Y; HA,
Hydroxyapatite; HOMO, Highest occupied molecular orbital; LUMO, Lowest unoccupied molecular orbital; St, Starch; Dex, Dextrin; CL, Cellulose; CS, Chitosan; CB, Conduction band; VB,
Valence band; ALG, Alginate; Dext, Dextran; DR, Direct red; DBD, Direct blue dye; RG, Rhodamine G; BV, Basic violet; PACAA, Poly(amidoamine-co-acrylic acid); PSMA, Poly(styrene-alt-
maleic anhydride); PNVCCMA, Poly(N-vinyl caprolactam-co-maleic acid); PANCS, Poly(acrylonitrile-co-styrene); PAANAF, Poly(anthranilic acid/4-nitroaniline/formaldehyde); PTh,
Polythiophene; PEI, Polyethelenamine; PPy, Polypyrrole; RHA, Rice husk ash; MPSAMA, Modified poly(styrene-alt-maleic anhydride); Te, Tenorite; P3MTh, Poly(3-methylthiophene);
PPDTh, Poly(3,4-propylenedioxythiophene); CPs, Conductive polymers; DMF, N, N-dimethylformamide; DMSO, Dimethyl sulfoxide; NMP, N-methylpyrrolidone; SDS, Sodium dodecyl
sulfate; CTAB, Cetyltri-methylammonium bromide; NPE, Nonylphenol ethoxylate; SAR, Sulfonated acid red; SA, Surfulamic acid; CA, Citric acid; TA, Taurine; TFZB, Thiol-functionalized
zeolite Beta; DI, Neutral deionized; PANI-ES, Polyaniline emeraldine salt; PoPDA, Poly(o-phenylenediamine); PProDOT, Poly(3,4-propylenedioxythiophene); APS, Ammonium persulfate;
AR, Acidic red; PmPDA, Poly(m-phenylenediamine); PpPDA, Poly(p-phenylenediamine); PVP, Poly(N-vinylpyrrolidone); HM, Hollow microspheres; PANICSP, Poly(aniline-co-m-sulfo-
phenylene diamine); PANICSA, Poly(aniline-co-5-sulfo-2-anisidine); Ani, Aniline; mSPD, m-sulfophenylene diamine; 5S2A, 5-sulfo-2-anisidine; PANDAN, Poly(aniline-co-1,8-diamino-
naphthalene); PPy-PANI, Poly(pyrrole-co-aniline); PANOA, Poly(aniline-co-o-aminophenol); pSmPDA, p-sulfonic-m-phenylenediamine; PAMpDA, Poly(aniline-co-m-phenylenediamine);
PA3ABA, Poly(aniline-co-3-aminobenzoic acid); PANIGCS, PANI grafted chitosan; CBB, Coomassie brilliant blue; CAc, Cellulose acetate; EPS, Extracellular polymeric substances; LC,
Lignocellulose; CALG, Calcium alginate; NMANI, N-methylaniline; NEANI, N-ethylaniline; 2EANI, 2-ethylaniline; PEG, Polyethylene glycol; PS, Polystyrene; PAM, Polyamide; PVA,
Polyvinyl alcohol; PET, Poly(ethylene terephthalate); MMS, Magnetic mesoporous silica; TCATS, Thiacalix[4]arene tetrasulfonate; PAmABAmPD, Poly(aniline-co-m-aminobenzoicacid-
co-m-phenylenediamine); HMS, Hexagonal mesoporous silica; NS, Natural silica; ZSP, Zirconium (IV) silicophosphate; LDHs, Layered double hydroxides; RGO, Reduction graphene oxide;
AC, Active carbone; N.R, No reported; PANINTs, Polyaniline nanotubes
⁎
Coresponding author.
E-mail addresses: ehsan.nazarzadehzare@gmail.com, e.nazarzadeh@du.ac.ir (E.N. Zare).

https://doi.org/10.1016/j.envres.2017.12.025
Received 25 October 2017; Received in revised form 7 December 2017; Accepted 28 December 2017
Available online 09 January 2018
0013-9351/ © 2017 Elsevier Inc. All rights reserved.
E.N. Zare et al.
1. Physical pollutants mainly influence the physical appearance or
other physical properties of water (e.g., sediment or material sus-
pended in the water from erosion of soil).
2. Chemical pollutants are elements or compounds, which can be
naturally occurring or man-made (e.g., bleach, pesticides, metals,
drugs, cosmetics, phytosanitary products, insecticides).
3. Biological pollutants are microbes or microbiological pollutants
(e.g., bacteria, viruses, and parasites).
4. Radiological pollutants are chemical elements with unstable atoms
that can emit ionizing radiation (e.g., cesium, plutonium and ur-
anium).
1.2. Heavy metals
Heavy metals are elements with atomic weights between 63.5 and
200.6, and a specific gravity greater than 5.0 (Fu and Wang, 2011;
Srivastava and Majumder, 2008). Nowadays, the heavy metal pollution
of wastewater is the most important environmental problem threa-
tening human life throughout the world due to the mobility of these
pollutants in natural water ecosystems and their toxicity.
With the rapid development of industries such as mining, metal
plating, tanneries, batteries, fertilizers, pesticides and paper industries,
heavy metal ions are directly or indirectly discharged into rivers, lakes,
or ocean environments (Sud et al., 2008). The heavy metal ions are
stable environmental contaminants since they cannot be degraded and
destroyed (Demirbas, 2008). Toxic heavy metals ions, such as arsenic,
copper, zinc, nickel, cadmium, chromium, mercury and lead can be
harmful to water and also remain a serious public health problem.
Some heavy metals, such as copper, zinc, iron, and manganese are
vital to the body in very low doses. However, if they are stored in the
body in concentrations sufficient to cause poisoning, drastic destruction
may occur. The following diseases are examples of poisoning caused by
heavy metals (Fu and Wang, 2011; Huang et al., 2014):
Arsenic (As): As can cause lung and skin cancers.
Mercury (Hg): Hg can cause impairment of pulmonary and kidney
function, chest pain and dyspnea.
Chromium (Cr): Cr can accumulate in food chain and alter the
human physiology. It can cause severe health problems ranging
from simple skin irritation to lung cancer.
Lead (Pb): Pb can cause severe dysfunction in the kidneys, liver and
reproductive system.
Nickel (Ni): Ni, known as a human carcinogen, can cause dermatitis
and allergic sensitization, lung and kidney problems.
Cadmium (Cd): Cd can cause high blood pressure, kidney damage,
and destruction of testicular tissue, osteoporosis and destruction of
red blood cells.
Cobalt (Co): Co can cause vomiting, nausea, diarrhea, asthma,
pneumonia, kidney congestion, skin degeneration and weight loss.
Copper (Cu): Cu can cause vomiting, diarrhea, stomach cramps,
and nausea, or even death.
1.3. Dyes
A dye can generally be described as a colored substance that has an
affinity to the substrate to which it is being applied (Yagub et al., 2014).
Dyes have an aromatic molecular structure, which probably comes from
hydrocarbons, such as toluene, benzene, anthracene, naphthalene, xy-
lene, etc. (Gong et al., 2005; Gupta et al., 2013). They have two key
components: the chromophores, which produce the color, and the
auxochromes, which are attached to a chromophore and modify its
ability (Gupta and Suhas, 2009).
There are two major types of dyes including natural and synthetic
dyes (Karadag et al., 2007; Sharma et al., 2011). The natural dyes are
extracted from natural substances, such as plants, animals, or minerals
(Vankar, 2000). Synthetic dyes are made in a laboratory and used in the
174
Environmental Research 162 (2018) 173–195
textile industry (Forgacs et al., 2004; Venkataraman, 1971). They are
largely classified as basic, direct, vat, reactive, azoic, sulfur, mordant,
acid, disperse, oxidation, mineral, and pigment dyes (Forgacs et al.,
2004; Venkataraman, 1971).
In addition to the above-mentioned classification, dyes are also
classified based on their particle charge upon dissolution in aqueous
medium as cationic (all basic dyes), anionic (direct, acid, and reactive
dyes), and non-ionic (disperse dyes) (Attia et al., 2006; Hameed et al.,
2007; Mall et al., 2006). Much concern has been expressed regarding
the use of dyes, due to their reported toxic effects. They can cause
mutagenesis, chromosomal fractures, carcinogenesis, and respiratory
toxicity (Srivastava et al., 2004). Therefore, according to the above-
mentioned diseases resulting from heavy metal ions and dyes, research
into the specific methods and technologies to remove heavy metal ions
and dyes from wastewater/aqueous solutions is desired.
1.4. Appropriate methods for the removal of heavy metal ions/dyes
Many techniques such as, ion-exchange, physical and chemical
precipitation, membrane filtration, electrochemical treatment, reverse
osmosis, solvent extraction, and adsorption processes are extensively-
used methods for removing heavy metal ions from wastewater/aqueous
solutions (Bulut, 2007; Demirbas, 2008).
On the other hand, some approaches such as, chemical oxidation,
coagulation, electrochemistry, aerobic and anaerobic microbial de-
gradation, membrane separation, and adsorption have been applied to
removing dyes from wastewater/aqueous solutions (Gupta et al., 2013;
Malik and Sanyal, 2004).
Among various techniques for removing heavy metal ions and dyes
from wastewater/aqueous solutions, adsorption is considered one of the
most possible and effective techniques for water treatment (Lakouraj
et al., 2014a, 2014b). Adsorption has been found to be superior to other
methods in terms of the flexibility and simplicity of design, initial cost,
ease of operation and insensitivity to toxic pollutants. In addition, it
does not result in the formation of harmful substances (Hua et al., 2012;
Rafatullah et al., 2010).
1.4.1. Effective factors on the adsorption of heavy metal ions/dyes
There are many factors affecting the adsorption of heavy metal ions
and dyes. These factors include the pH of solution, adsorbent dosage,
contact time, concentration of initial heavy metal ions/dyes, and tem-
perature (Yagub et al., 2014; Zare et al., 2016, 2015b). The optimiza-
tion of these conditions can significantly help in the development of
heavy metal ions/dyes removal.
1.4.1.1. pH. The variations in pH can determine the ionization degree
of an adsorptive molecule as well as the surface properties of an
adsorbent (Nandi et al., 2009; Yagub et al., 2014; Zare et al., 2015b), so
the initial pH of a solution is a significant and imperative factor
affecting the capacity of an adsorbent in water treatment.
Furthermore, the dependence of sorption on pH is associated with
both the metal and dye chemistry in the solution and the ionization
state of the functional groups of the sorbent (Yagub et al., 2014).
1.4.1.2. Adsorbent dosage. A material which has the capability of
adsorbing molecules of gases, liquids, or solids without any physical
or chemical change is called an adsorbent (Dąbrowski, 2001). The
adsorbent amount is an important factor controlling the adsorbent
capacity for a certain amount of an adsorbent at the operating
conditions (Zare et al., 2016, 2015b). The removal percentage usually
increases as the adsorbent amount increases. In fact, the sorption sites
at the adsorbent surface increase by increasing the amount of the
adsorbent, so this factor provides an idea for the ability of a metal/dye
adsorption to be adsorbed with the minimum amount of the adsorbent
(Yagub et al., 2014).
E.N. Zare et al. Environmental Research 162 (2018) 173–195

Table 1
The reported studies for the removal of heavy metal ions/dyes by agricultural residue materials.

Agricultural residue Pollutant Q (mg/g) Reference

Rice husk CR, Cd(II) 103, 461 (Ajmal et al., 2003; Han et al., 2008)
Walnut shell RB, Pb(II), Ni(II), Cu(II) 2.29, 9.34, 8.57, 204.08 (Karimi-Jashni and Saadat, 2014; Shah et al., 2013; Wolfová et al., 2013;
Xie et al., 2013)
Orange peel AD, Cu(II), Co(II), Ni(II), Zn(II), Pb 5.6–18.3, 3.65, 1.82, 6.01, 5.05, 7.75 (Do Nascimento et al., 2014; Annadurai et al., 2015)
(II)
Sunflower seed shells DD, Pb(II) 0.87, > 90 (Osma et al., 2007; Saka et al., 2012)
Eggshell MB, Cu(II), Fe(II) 113.6, N.R (Agarwal and Gupta, 2014; Tsai et al., 2008)
Sawdust MB, Pb(II), Cd(II), Ni(II) 5.78, 6.54, 4.39, 2.40 (Bulut, 2007; Rao and Rao, 2013)
Pomegranate peel DBD 106, Pb(II), Cu(II) 25.54–58.14, 5.6, 5.8 (Amin, 2009; El-Ashtoukhy et al., 2008)
Carrot pulp Cr(III), Cu(II), Zn(II) 45.09, 32.74, 29.61 (Nasernejad et al., 2005)
Soybean ADAO 7 N.R (Gupta et al., 2006)
Cottonseed hulls NR 176.9 (Zhou et al., 2011)
Olive stone Safranine, Cd(II) 526.3, 128.2 (Aziz et al., 2009)
Fly ash BD, Pb(II), Cu(II), Zn(II), Mn(II), Cd 4.47, 0.06, 0.04, 0.03, 0.01, 0.09 (Alinnor, 2007; Mohan and Gandhimathi, 2009; Wang et al., 2005)
(II)

1.4.1.3. Contact time. The contact time helps in identifying the possible
speed of binding and the removal of hazardous pollutants. The contact
time is an essential parameter for the impressive use of an adsorbent for
practical applications and finding the optimum time for the complete
removal of the particular metal/dye (Yavuz et al., 2011; Zare et al.,
2016, 2015b). Generally, the adsorption efficiency increases by
increasing the contact time to reach the optimum time, then remains
almost constant thereafter.
1.4.1.4. Initial concentration of heavy metal ions/dyes. The initial
concentration of heavy metal ions/dyes is an important parameter on
the adsorption rate to describe an effective adsorption (Bulut and
Aydın, 2006; Norouzian and Lakouraj, 2015a; Zare et al., 2015b). The
adsorption amount of a heavy metal/dye is effectively dependent on the
initial concentration of the heavy metal/dye. The effect of initial
concentrations of heavy metal ions/dyes depends on the possible
interactions between the heavy metal ions/dyes concentration and
the accessible sites on the surface of an adsorbent (Yagub et al., 2014).
Generally, the removal percentage decreases with an increase in the
initial concentration of heavy metal/dye, which is probably due to the
saturation of the adsorption sites on the surface of the adsorbent. On the
other hand, an increase in the initial concentration of heavy metal/dye
will cause an increase in the adsorbent capacity. This is probably due to
the high driving force for mass transfer at high initial concentrations of
the heavy metal/dye (Yagub et al., 2014).
1.5.1. Agricultural residue
Agricultural residue materials are usually composed of lignin and
cellulose as the main constituents. Other components are extractives,
lipids, hemicellulose, proteins, starches, simple sugars, ash, hydro-
carbons, and many more compounds that contain a variety of functional
groups present in the binding process (Hashem et al., 2007, 2005; Sud
et al., 2008). Several agricultural residue materials including, rice husk,
walnut shell, orange peel, sunflower seed shell, eggshell, sawdust, po-
megranate peel, carrot pulp, soybean and cottonseed hulls, olive stone,
and fly ash have been used for the removal of heavy metal ions/dyes
from wastewater/aqueous solutions (Agarwal and Gupta, 2014; Ajmal
et al., 2003; Alinnor, 2007; Amin, 2009; Annadurai et al., 2015; Aziz
et al., 2009; Bulut and Tez, 2007; Do Nascimento et al., 2014; El-
Ashtoukhy et al., 2008; Gupta et al., 2006; Han et al., 2008; Karimi-
Jashni and Saadat, 2014; Mohan and Gandhimathi, 2009; Nasernejad
et al., 2005; Osma et al., 2007; Rao and Rao, 2013.; Saka et al., 2012;
Shah et al., 2013; Tsai et al., 2008; Wang et al., 2005; Wolfová et al.,
2013; Xie et al., 2013; Zhou et al., 2011). Table 1 shows the reported
studies for the removal of heavy metal ions/dyes by agricultural residue
materials. Accordingly, the agricultural residues are effective ad-
sorbents for the removal of various pollutants from water. The highest
and lowest adsorption capacities are related to the olive stone (526 mg/
g for Safranine) and the fly ash (0.01 mg/g for Mn(II)), respectively.
Also, the results show that the agricultural residues are generally better
adsorbents for the removal of heavy metal ions than dyes.

1.4.1.5. Temperature. Temperature is an important parameter that can
change the adsorption capacity of the adsorbent. Adsorption is an
endothermic process if the adsorption dosage increases with increasing
temperature (Argun et al., 2008; Yagub et al., 2014). In this case, higher
temperatures will probably lead to the higher mobility of the heavy
metal ions/dye molecules and more active sites for the adsorption as
well (Chiou and Li, 2003; Li et al., 2005; Netpradit et al., 2004). On the
other hand, the decrease of the adsorption capacity with increasing
temperature indicates that the adsorption is an exothermic process. In
this case, the adsorptive forces between the heavy metal ions/dye
molecules as well as the active sites on the surface of the adsorbent
decrease as a result of decreasing the amount of the adsorbent (Chiou
and Li, 2003; Li et al., 2005; Netpradit et al., 2004).
1.5. Adsorbents and nanoadsorbents
Nanoadsorbents are commonly defined as having at least one di-
mension in the range of 1 – 100 nm. Adsorbents can be classified in four
types based on their source, as agricultural residue, inorganic, poly-
meric and composite.
1.5.2. Inorganic and organic nanoadsorbents
Metal oxide nanoparticles including TiO2, SiO2, MnO, ZnO, and
Fe2O3, carbon nanotubes (CNTs), graphene (G), graphene oxide (GO),
zeolites, and hydroxyapatite are currently the most widely used ad-
sorbents for the removal of heavy metal ions/dyes from wastewater/
aqueous solutions (Ada et al., 2009; Afkhami and Moosavi, 2010; Alver
and Metin, 2012; Bang et al., 2005; Ciobanu et al., 2014; Erdem et al.,
2004; Gong et al., 2009; Gupta et al., 2011; Heidari et al., 2009; Kandah
and Meunier, 2007; R. Kumar et al., 2013; K.Y. Kumar et al., 2013; Lu
and Chiu, 2006; Mishra et al., 2010; Parga et al., 2013; Ramesha et al.,
2011; Sheela et al., 2012; Sitko et al., 2013; Tsai et al., 2004; Wei et al.,
2015; Wingenfelder et al., 2005; Yao et al., 2010; Zhong et al., 2006).
Table 2 displays the reported studies for the removal of heavy metal
ions/dyes by inorganic and organic nanoadsorbents. Accordingly, the
inorganic and organic particles are more effective adsorbents than the
agricultural residues (Table 1) for the removal of various pollutants
from water, and their adsorption capacity for various contaminants is
between 0.003 and 1119 mg/g. The structure of the adsorbents and
their size are important factors for the adsorption capacity.

175
E.N. Zare et al.
Table 2
The reported studies for the removal of heavy metal ions/dyes by inorganic and organic nanoadsorbents.
Inorganic adsorbents Pollutant
TiO2 Tartrazine, As(V), As(III)
SiO2 MB, Pb(II), Ni(II), Cd(II)
ZnO MGO, RBBR, Cr(VI), Zn(II), Cd(II), Hg(II)
CNTs AD, CD, MB, Ni(II), Zn(II)
G an GO MB, MV, RB, OG, Pb(II), Cu(II), Cd(II), Zn
(II),
Fe3O4 CR, As(V), Cr(VI)
Zeolite RR 239, RB 250, Co(II), Cu(II), Zn(II), Mn
(II), Pb(II), Fe(II)
HA AB 172, MB, Cu(II), Pb(II)
1.5.3. Polymeric adsorbents
In recent decades, polymeric adsorbents have emerged as potential
alternatives to traditional adsorbents in terms of their vast surface area,
adjustable surface chemistry, perfect mechanical rigidity, pore size
distribution, and feasible regeneration under mild conditions
(Mahmoodi et al., 2013). Commonly, polymeric materials can effec-
tively adsorb many pollutants. Generally, polymeric adsorbents can be
categorized into two major types as carbohydrate polymers and func-
tionalized synthetic polymers.
1.5.3.1. Carbohydrate polymers. Carbohydrate molecules, i.e., starch,
dextran, chitosan, cellulose, alginate, etc. are composed of long chains
of monosaccharide units bound together by glycosidic linkages which
on hydrolysis give the constituent monosaccharides or oligosaccharides
(Lendlein and Sisson, 2011). They are widely used as adsorbents for the
removal of heavy metal ions/dyes from wastewater/aqueous solutions
(Cheng and Ou, 2016; J. Li et al., 2015; S. Li et al., 2015; X. Li et al.,
2015; K. Li et al., 2015; Lu et al., 2015; Medeiros Borsagli et al., 2015;
Mosaferi et al., 2014; Srinivasan et al., 2016; Wang and Li, 2013; Yu
et al., 2013). Table 3 shows the reported studies for the removal of
heavy metal ions/dyes by carbohydrate polymers. According to Table 3,
the carbohydrate polymers can be used as effective adsorbents for the
removal of pollutants due to their hydroxyl, amine, amide and carboxyl
functional groups. The highest adsorption capacity is related to
alginate. It seems that the carboxyl functional groups in the alginate
structure are more effective chelating groups than other functional
groups.
1.5.3.2. Functionalized synthetic polymers. The adsorption capacity of
synthetic polymers toward contaminations can be improved using
monomers with functional groups such as amino and carboxylic
groups, which can be due to the specific interactions between the
functional groups, bound to the polymeric matrices, and the target
contaminations (Mahmoodi et al., 2013). Functionalized synthetic
polymer adsorbents consist of two main parts: the chelating
functional groups and the polymer matrix (Moghadam et al., 2013).
Various functionalized synthetic polymers, such as poly(amidoamine-
co-acrylic acid), poly(styrene-alt-maleic anhydride), poly(N-vinyl
caprolactam-co-maleic acid), poly(acrylonitrile-co-styrene), poly
(styrene-co-maleic acid), and poly( anthranilic acid/4-nitroaniline/
Table 3
The reported studies for the removal of heavy metal ions/dyes by carbohydrate polymers.
Carbohydrate polymers Pollutant
Starch As(V), As(III), Cu(II), Pb(II), Cr(VI),
Dextran Cu(II)
Cellulose C.I. RR 228, Cd(II), Pb(II)
Chitosan Cr(VI), Cd(II),
Alginate MB, Cu(II), Ag(I), Fe(III),
Environmental Research 162 (2018) 173–195
Q (mg/g) References
N.R, 41.4, 32.4 (Bang et al., 2005; Gupta et al., 2011)
50, 57.74, 12.36, 18.25 (Heidari et al., 2009; Tsai et al., 2004)
310.50, 345, 9.38, 357, 387, 714 (Ada et al., 2009; R. Kumar et al., 2013; K.Y. Kumar et al., 2013;
Sheela et al., 2012)
141–152, 6.28–11.86, 35.4–64.7, (Gong et al., 2009; Kandah and Meunier, 2007; Lu and Chiu, 2006;
18.08, 32.68 Mishra et al., 2010; Yao et al., 2010)
17.3, 2.47, 1.24, 5.98, 1119, 294, (Ramesha et al., 2011; Sitko et al., 2013)
530, 345
208.33, 4.65, 4.38 (Afkhami and Moosavi, 2010; Zhong et al., 2006)
0.68, 1.05, 0.01, 0.008, 0.008, (Alver and Metin, 2012; Erdem et al., 2004; Wingenfelder et al.,
0.003, N.R, N.R 2005)
312.5, 14.27, N.R, N.R (Ciobanu et al., 2014; Parga et al., 2013; Wei et al., 2015)
formaldehyde) have been used for water treatment (Azarudeen et al.,
2016; El-Aassar et al., 2016; Li et al., 2016; Mahmoodi et al., 2013;
Moghadam et al., 2013; Popescu and Suflet, 2016). Table 4 reports the
studied works for the removal of heavy metal ions/dyes by
functionalized synthetic polymers. As seen in Table 4, the
enhancement of the adsorption capacity is directly related to the
chelating groups in the polymer structures. The PACA polymer has
the maximum adsorption capacity.
1.5.4. Composite and nanocomposite adsorbents
Composite/nanocomposite materials are another group of ad-
sorbents used mainly for the removal of heavy metal ions/dyes from
wastewater/aqueous solutions. Composite/nanocomposite materials
display better adsorption capacities, granulometric properties, chemical
and thermal stabilities, reproducibilities, and also have better se-
lectivities for the heavy metal ions/dyes removal compared to pure
organic and inorganic materials (Sharma et al., 2015). A number of
composite/nanocomposite adsorbents have been introduced so far for
the removal of heavy metal ions/dyes (Deng et al., 2013; Ebadi et al.,
2016; Hashemian et al., 2015; Ren et al., 2012; Samadi et al., 2016;
Xing et al., 2015; Zeng et al., 2015; Zhang et al., 2015). Adsorbents-
based polymer nanocomposites have some distinctive properties, such
as easy preparation, cost-effectiveness, environmental stability, effec-
tive binding sites along the walls of the polymers with large surface
area, and pore volume.
Among polymer nanocomposites, conducting polymer-based ad-
sorbents, such as polyaniline (PANI) and its derivatives, polythiophene
(PTh), polyethelenamine (PEI), polypyrrole (PPy) and their nano-
composites have received significant attention due to their potential
applications in adsorbing various heavy metal ions/dyes, ease of
synthesis, porous structure, regeneration, non-toxicity, insolubility in
water, environmental and mechanical stability, and low cost (Ansari
and Delavar, 2009; Ansari and Mosayebzadeh, 2010a, 2010b, 2010c;
Ansari et al., 2013, 2011, 2008; Ballav et al., 2012; Bhaumik et al.,
2016, 2011; Chen et al., 2015; Ghorbani and Eisazadeh, 2012; Hasani
and Eisazadeh, 2013; Hena, 2010; Jamal et al., 2016; Javadian and
Taghavi, 2014; Khalili et al., 2014; Li et al., 2013; Omraei et al., 2011;
Srivastava et al., 2015; Zare et al., 2015a, 2014). Table 5 shows the
reported studies for the removal of heavy metal ions/dyes by some
conductive polymer-based adsorbents. According to Table 5, it can be
Q (mg/g) References
14, 12, 29, 65, 12 (Cheng and Ou, 2016; Mosaferi et al., 2014)
N.R (J. Li et al., 2015; S. Li et al., 2015; X. Li et al., 2015; K. Li et al., 2015)
190, 259–344, 367–451 (Wang and Li, 2013; Yu et al., 2013)
9.42, 80 (Medeiros Borsagli et al., 2015; Srinivasan et al., 2016)
572, 54.9, 82.8, 135.5 (Lu et al., 2015)
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Table 4
The reported studies for the removal of heavy metal ions/dyes by functionalized synthetic polymers.

Functionalized synthetic polymers Pollutant Q (mg/g) References

PACAA DR 31, DR 80, AB 25 3400, 3448, 3500 (Mahmoodi et al., 2013)

PSMA MB, RB, Zn(II), Cu(II), Fe(II) 344.83, 671.14, 15.03, 5.21, 24.50 (Li et al., 2016; Moghadam et al., 2013)
PNVCCMA R6G, MB 2012, 1441 (Popescu and Suflet, 2016)
PANCS C.I. BV 16 32.5 (El-Aassar et al., 2016)
PAANAF Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Pb(II) 9, 6.62, 5.32, 7.14, 4.05, 7.64 (Azarudeen et al., 2016)

concluded that the existence of N and S atoms in the main chain
structure of the conductive polymers is responsible for the pollutant
adsorption. Also, N atoms in polypyrrole result in the higher adsorption
capacity than the S atoms in polythiophene.
This review describes a summary of several nanoadsorbents based
on polyaniline and its derivatives for the removal of heavy metal ions/
dyes from wastewater/aqueous solutions. The synthesis method, pH
and temperature effects, percentage of removal, and adsorption capa-
city of the adsorbents are discussed in this section.
2. Nanoadsorbents based on polyaniline and its derivatives
2.1. Polyaniline and its derivatives
Among the conductive polymers (CPs), PANI and its derivatives
have attracted great attention due to facile synthesis, electrical con-
ductivity, low cost, and environmental stability (Lakouraj et al., 2014c;
Moghadam and Zareh, 2010; Zareh and Moghadam, 2011). PANI de-
rivatives have the same chemical structure to PANI with different
pendant functional groups at ortho, meta and para positions relative to
the amine group of PANI. In comparison to PANI, PANI derivatives have
shown good solubility in common organic solvents, such as N, N-di-
methylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methyl-
pyrrolidone (NMP) but with poor conductivity. PANI and its derivatives
have been synthesized via the polymerization of the corresponding
monomers in the presence of a peroxy initiator under acidic conditions.
PANI derivatives show more multifunctionality than PANI due to one
pendent active functional group per repetitive unit on the polymer
chains (Lakouraj et al., 2014c). PANI and its derivatives have also
displayed good adsorption capability due to their large amount of
amine and imine functional groups in the polymer chains, so they are
used as adsorbents for the removal of heavy metal ions/dyes from
wastewater/aqueous solutions. Recently, various studies have been
done on PANI and its derivatives as effective nanoadsorbents for the
removal of heavy metal ions/dyes.
2.1.1. PANI
Ai et al. utilized uniform PANI microspheres as an adsorbent for
methyl orange removal. It was demonstrated that the monolayer ad-
sorption capacity of PANI microspheres was 154.56 mg/g at pH above 6
(Ai et al., 2010). It was also reported that, at the beginning, the ad-
sorption mainly occurs on the surface of PANI microspheres, so the
adsorption rate is fast. After the surface adsorption is saturated, the
adsorption gradually proceeds into the inner part of PANI microspheres
via the diffusion of MO into the polymer matrix leading to a lower
adsorption rate.
Wang et al. also evaluated the PANI particles for Hg(II) removal
from aqueous solutions. It was found that the adsorption capacity of
PANI particles was 600 mg/g for Hg(II) ions. Furthermore, pH 5.5 was
proper for high adsorption of Hg(II) ions due to the fact that all the
nitrogen-containing functional groups on the polymer matrix including
imine, protonated imine and amine could be responsible for mercury
adsorption (Wang et al., 2009).
Riahi Samani et al. reported the adsorption of Cr(VI) ions in aqueous
solutions by PANI particles. They concluded that the type of the solvent
used for the synthesis of PANI had a special effect on the capacity of
PANI for Cr(VI) removal from aqueous solutions and on the morphology
of PANI as well. The synthesized PANI in water also had the maximum
Cr(VI) removal efficiency (above 90%). Based on the examinations,
they concluded that the removal mechanism involving PANI was the
combination of surface adsorption and reduction (Riahi Samani et al.,
2011).
Mahanta et al. demonstrated the ability of PANI emeraldine salt
synthesized by chemical oxidation to adsorb OG dyes. They suggested a
mechanism based on the chemical interaction of PANI with the sulfo-
nate group of the OG dyes. It was observed that the percentage removal
of the OG dye was complete (100%) at lower OG concentrations (below
100 ppm) and pH 3.39. (Mahanta et al., 2008).
Kumar et al. studied the synthesis of short chain PANI (oligoaniline)
for the removal of Cr(VI) from aqueous solutions by oxidation of aniline
in the presence of 1,4-phenylenediamine, as a chain terminator in

Table 5
The reported studies for the removal of heavy metal ions/dyes by some conductive polymer-based adsorbents.

Conductive polymer-based Pollutant Q (mg/g) References

adsorbents

PPy Cd(II) 9.70 (Hasani and Eisazadeh, 2013)

PPy/Fe3O4 Fluoride 17.6–22.3 (Bhaumik et al., 2011)
Glycine doped PPy Cr(VI) 217.39–232.55 (Ballav et al., 2012)
PPy/Fe3O4 Cr(VI) 169.4–243.9 (Bhaumik et al., 2016)
PPy/TFZB/MCM-41 Hg(II) 157.43 (Javadian and Taghavi, 2014)
PPy/SD Cr(VI), Zn(II), EY, MB N.R, 28.04 , 3.09, 34.36 (Ansari and Mosayebzadeh, 2010a, 2010b; Ansari et al., 2011;
Omraei et al., 2011)
PPy/RHA Zn(II), Cu(II), Fe(II), Mn(II) N.R (Ghorbani and Eisazadeh, 2012)
PPy/MPSAMA Cu(II), Pb(II), Cd(II) N.R (Zare et al., 2015a)
PPy/TiO2 MB 323.62 (Li et al., 2013)
PPy/Tenorite Tartrazine, Pb(II), Cd(II), Zn(II), Co(II), 42.50, N.R (Srivastava et al., 2015)
Mn(II)
P3MTh/SD MB, Ag(I), As(III) 191, 2.45, 0.28 (Ansari and Delavar, 2009; Ansari et al., 2013, 2008)
CS/P3MTh Cr(VI) 127.62 (Hena, 2010)
PThu/TiO2 Pb(II) 151.5–173.6 (Chen et al., 2015)
PTh/Sb2O3 Pb(II) 18.94 (Khalili et al., 2014)
PProDOT/MnO2 MB 13.94 (Jamal et al., 2016)

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acidic aqueous medium. They found that the maximum monolayer
capacity of oligoaniline for Cr(VI) was 62.9 mg/g at pH 3 and 20 °C. On
the other hand, they observed that total chromium adsorption de-
creased with rising temperature suggesting an exothermic adsorption of
chromium binding on –NH2 sites of PANI (Kumar et al., 2008).
The adsorption of cationic MB dye from aqueous solutions onto
PANI nanotubes was also studied by Ayad et al. and it was found that
the adsorption capacity of PANI nanotubes was 4.8 mg/g at pH 10.01. It
was reported that the MB adsorption on the PANI nanotubes was much
higher than that on the conventional PANI powder. This was due to the
increases in the surface area of the substrate, so the PANI NTs provide
more efficient adsorbent than PANI powder substrates (Ayad and El-
Nasr, 2010).
Baruah et al. used the PANI emeraldine salt (PANI-ES) particles as
an adsorbent for the removal of Cr(VI) ions from aqueous medium. It
was seen that the removal of Cr(VI) was negligibly affected by the
presence of other anions in the aqueous medium. The adsorption ca-
pacity of PANI-ES was found to be 123.21 mg/g, which was very high
compared to activated carbon-based materials (Baruah and Mahanta,
2016).
Yan et al. studied the adsorption of MB dye onto PANI hydrogel
fabricated by using phytic acid as both dopant and cross-linking agent.
They found that, with the increase of pH, the adsorption capacity of
PANI hydrogel for MB had a significant increasing trend, while it had
low adsorption capacities for MB when the pH was lower than 3. It was
attributed to the fact that the adsorbent had a more positive potential
on the surface when the pH value was lower. The maximum adsorption
(71.2 mg/g) was at a pH value of 6.5 (Yan et al., 2015). Based on the
adsorption behaviors and the chemical properties of the adsorbent and
adsorbate, they proposed an adsorption mechanism for MB adsorption
on the PANI hydrogel, as shown in Fig. 1. It seems that the electrostatic
forces between the MB cationic dye and the PANI emeraldine base lead
to the MB adsorption on the PANI hydrogel.
Bai et al. studied the adsorption of both anionic (methyl orange,
congo red, orange-G) and cationic dyes (methylene blue, rhodamine-B,
malachite green) from aqueous solutions using synthesized acid doped
PANI with hydrochloric acid and p-toluenesulfonic acid. They carried
out all the experiments at pH 5 in which the maximum dye adsorption
was observed for doped PANI. They found that the acid-doped PANI
could be employed as a promising adsorbent for the removal of anionic
dyes from wastewater. Also, a very good selectivity was reported for the
OG dye, and the proposed mechanism was based on the chemical in-
teractions between PANI and the sulfonate group of the dyes (J. Li et al.,
2015; S. Li et al., 2015; X. Li et al., 2015; K. Li et al., 2015).
Ahmed et al. reported the use of nano PANI fabricated by chemical
Fig. 1. Acceptable adsorption mechanism for the removal of MB dye by PANI hydrogel
(Baruah and Mahanta, 2016).
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oxidation in the presence of different types of commercial surfactants,
i.e., sodium dodecyl sulfate (SDS), cetyltri-methylammonium bromide
(CTAB) and nonylphenol ethoxylate (NPE) for treatment of sulfonated
AR 14 from aqueous solutions. It was found that the rate of dye removal
increased by increasing the amount of PANI (NPE), but decreased by
increasing the initial dye concentration. According to the chemical in-
teraction between the SO3- groups on the dye and the positively charged
backbone of nano PANI, they suggested an adsorption mechanism for
AR adsorption on the PANI nanoparticles (Ahmed et al., 2012).
Wang et al. examined PANI nanoparticles and one-dimensional
nanostructures constructed by a sono-assisted chemical oxidation
method in protonic acids like HCl, surfulamic acid (SA), citric acid
(CA), taurine (TA) and neutral deionized (DI) water for the sorption of
Cr(VI) ions. It was reported that all the prepared PANI nanostructures
showed efficient adsorption for Cr(VI), but their adsorption efficiencies
varied depending on the protonic acids and the consequent molecular
structures of PANIs. Also, the PANI-HCl showed the highest adsorption
capacity, followed in descending order by PANI-SA, PANI-CA, PANI-TA
and PANI-DI. It was also observed that the adsorption capacity corre-
lated well with the oxidation state and protonation extent of PANIs; and
the pH of the solution had an obvious effect on Cr(VI) adsorption,
especially for PANI-TA and PANI-DI. A mechanism of electrostatic ad-
sorption proposed by the reduction of Cr(VI) to Cr(III) was proposed by
analyzing FTIR, zeta potential and XPS spectra of PANIs before and
after Cr(VI) adsorption (Jing Wang et al., 2014). Fig. 2 shows SEM and
TEM images of various PANI nanostructures. Table 6 shows data on the
sorption of heavy metals and dyes by PANI. Fig. 2 and Table 6 show
that different structures of PANI, which can be synthesized by various
methods, can change the pollutants adsorption.
2.1.2. Poly(Ortho-Phenylenediamine) (PoPDA)
Li et al. investigated the sorption of Ag(I) and Hg(II) ions by PoPDA
microspheres synthesized via the chemical polymerization of oPDA
monomers by ammonium persulfate (APS) at room temperature. It was
reported that the Ag(I) adsorption steadily increased with a changing
oxidant/monomer molar ratio from 3/1 to 1/1, reaching a highest Ag(I)
adsorption level of 533 mg/g at the oxidant/monomer ratio of 1/1 with
the highest adsorptivity of Ag (I) ions up to 99.1% at pH around 5.0.
They proposed that the sorption mechanism may include the chelation
and redox reaction between Ag(I) ions and amine/imine groups on the
PoPD chains. In addition, the competitive sorption between Ag(I) and
Hg(II) in their mixture solution onto the PoPDA microparticles ex-
hibited a preferential sorption toward Ag(I) (Li et al., 2009a, 2009b).
On the other hand, Wang et al. synthesized PoPDA microspheres
through chemical polymerization of oPDA monomers by ammonium
persulfate (APS) at room temperature for the removal of Cr(VI) ions
from aqueous solutions. They studied the Cr(VI) adsorption behavior on
the prepared PoPDA microspheres at various adsorption contact times,
pH values, and amount of the adsorbent. The maximum adsorption
capacity 98.23 mg/g for PoPDA microspheres was reported at contact
time 1.5 h, pH less than 4 and amount of the adsorbent 0.4 g (Wang and
Liao, 2012).
Han et al. investigated two kinds of different-shaped PoPDA, i.e.,
solid and hollow sub-microspheres, with a size of about 700 nm fabri-
cated by a solution route without any additional directing agents, as
efficient adsorbents for the removal of Pb(II) ions from water. They
reported that both hollow and solid PoPDA sub-microspheres showed
high adsorption capacity towards Pb(II) ions in water. The adsorption
mechanism (Fig. 3) was proposed based on the XRD and X-ray photo-
electron spectrum (XPS). It was found that the pH of solution, con-
centration of Pb(II) ion, contact time, and adsorbent dosage affect the
degree of adsorption. The adsorption capacities by hollow and solid
PoPDA sub-microspheres were reported to be 103.20 and 101.32 mg/g,
respectively (Han et al., 2011).
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Fig. 2. SEM of the synthesized PANI nanotubes (A), PANI hydrogel (B), PANI nanosticks (C) and TEM of PANI nanoparticles (SDS) (D), PANI nanoparticles (CTAB) (E), PANI nanoparticles
(NPE) (F) (Ahmed et al., 2012; Ayad and El-Nasr, 2010; J. Li et al., 2015; S. Li et al., 2015; X. Li et al., 2015; K. Li et al., 2015; Yan et al., 2015).

2.1.3. Poly(m-phenylenediamine) (PmPDA)
Recently many researchers have synthesized PmPDA microparticles
by oxidative precipitation polymerization for the removal of Pb(II), Hg
(II), SO3-, MB, and Cr(VI) ions (Chai et al., 2014; Huang et al., 2006;
Sang et al., 2013; Tang et al., 2011; W. Yu et al., 2013b; X. Yu et al.,
2013). It was found that the degree of adsorption of the Pb(II), Hg(II),
SO3-, MB, and Cr(VI) ions were dependent on the pH, concentration,
and temperature of the solution, as well as the contact time and PmPDA
microparticle dose. They reported that the highest adsorptivity values
of Pb(II), Hg(II), SO3-, MB, and Cr(VI) ions were 99.8%, 97.83, 95.1%,
96.1%, and 96%, respectively.
Some studies reported the use of PmPDA nanoparticles fabricated by
various methods for the adsorption of Ag(I) and As(V) (Dai et al., 2015;
Meng et al., 2014; Su et al., 2014, 2013; Yu et al., 2013a, 2013b). Su
et al. synthesized PmPDA as nanorods and hollow nanostructures
through MeOH induction by conventional chemical oxidative and die-
thanolamine-assisted conventional oxidation polymerization, respec-
tively. It was reported that the adsorption capacities of Ag(I) onto
PmPDA nanorods and hollow nanostructures were 2073 and
2359.3 mg/g, respectively (Su et al., 2014, 2013). Fig. 4 displays a
possible growth route of PmPDA nanorods synthesized in MeOH media
(Su et al., 2013). Accordingly, the monomers are oxidized to cation

Table 6
Data on the sorption of heavy metal ions/dyes by PANI.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PANI microspheres MO above 6 25 154.56 N.R (Ai et al., 2010)

PANI particles Hg(II) 5.5 25 600 N.R (Wang et al., 2009)
PANI particles Cr(VI) 7 25 N.R above 90 (Riahi Samani et al., 2011)
PANI-ES OG 3.39 25 N.R 100 (Mahanta et al., 2008)
Short chain PANI Cr(VI) 3 20 62.9 above 70 (Kumar et al., 2008)
PANI nanotubes MB 10.01 25 4.8 N.R (Ayad and El-Nasr, 2010)
PANI-ES Cr(VI) Acidic 25 123.21 above 99 (Baruah and Mahanta, 2016)
PANI nanohydrogel MB 6.5 45 above 71.2 N.R (Yan et al., 2015)
PANI-ES nanoparticles OG 5 25 N.R above 99 (Li et al., 2015)
NanoPANI (SDS) 251 91 (Ahmed et al., 2012)
NanoPANI (CTAB) AR 4 25 256 93
NanoPANI (NPE) 266 97
NanoPANI-HCl Cr(VI) 2-6 25 N.R 100 (Wang et al., 2014b, 2014)
NanoPANI-SA 2-6
NanoPANI-CA 2-3
NanoPANI-TA 2
NanoPANI-DI 2

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radicals by the addition of an oxidant, and the electrophilic substitution
reaction is initiated with the formation of PmPD nanoparticles. The
polymerization rate in MeOH is slow in comparison to that in H2O, and
therefore, the growth of the nanoparticles is tardigrade.
Yu et al. used the conventional chemically oxidative polymerization
improved through the cooperative effect of Cu2+ and NaOH to synth-
esis the PmPD nanoparticles as an adsorbent for Ag(I) ions. A possible
mechanism was suggested based on in-situ open-circuit potential, pH
detections and Fourier transform infrared (FTIR) spectroscopy.
Moreover, the adsorption capacity of Ag(I) onto PmPD nanoparticles
was found to be 1767 mg/g (Yu et al., 2013a).
Dai et al. examined PmPD particles prepared via a new Cu-catalyzed
air oxidation method as an adsorbent for the removal of As(V) from
aqueous solutions. They showed that the higher loadings of Cu particles
exhibited an improved As(V) removal capability of 27.4 mg/g. The
possible mechanisms for the adsorption of As(V) onto PmPD particles
were explored using XPS (Dai et al., 2015).
Meng et al. applied uniform PmPDA nanobelts with high surface
area fabricated via the chemical oxidative polymerization of mPDA
using white cetyl trimethyl ammonium persulfate (CTAP) as an oxidant
for OG dye removal. They showed that PmPDA nanobelts had a superior
ability towards OG adsorption with a maximum adsorption of 460 mg/
g. It was indicated that the acid doping of PmPDA nanobelts had better
adsorption performance for OG dye (Meng et al., 2014).
2.1.4. Poly(p-phenylenediamine) (PpPDA)
Huang et al. and Archana et al. demonstrated the effective adsorp-
tion of Pb(II) and Cr(VI) onto PpPDA microparticles synthesized by
oxidative precipitation polymerization. They reported that the adsorp-
tion capacities and removal percentages of Pb(II) and Cr(VI) ions were
253.2 mg/g and 79.13%, respectively (Archana and Jaya Shanthi,
2015; Huang et al., 2006).
Min et al. introduced a novel method for the shape-controlled
synthesis of PpPDA microstructures using a UV lamp as the oxidation
energy source and poly(N -vinylpyrrolidone) (PVP) as the surfactant.
They demonstrated that, although PVP played an important role in
controlling the morphology of such polymer particles, it had no influ-
ence on the intrinsic polymer structures. It was observed that the
PpPDA polymer microstructures had excellent adsorption ability in the
removal of Pb(II) ions from wastewater with the highest adsorption
capacity above 800 mg/g (Min et al., 2011). Fig. 5 displays SEM and
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Fig. 3. Possible complexation between Pb(II) ions and PoPDA
polymers (Han et al., 2011).
TEM images of the synthesized PoPDA, PmPDA and PpPDA by various
methods (Archana and Jaya Shanthi, 2015; Dai et al., 2015; Han et al.,
2011; Meng et al., 2014; Min et al., 2011; Su et al., 2013; Wang and
Liao, 2012). Table 7 shows data on the sorption of heavy metal ions/
dyes by PANI derivatives. As mentioned, the morphology and chemical
structure of the conductive polymers affect the adsorption capacity. For
instance, the maximum Pb(II) adsorption on PANI derivatives is in the
order PpPDA microspheres > PmPDA microparticles > PoPDA hollow
microspheres (Table 7).
2.1.5. PANI copolymers
Copolymerization is one of the effective methods to achieve an
improved amount of amine groups on polymer chains, and therefore,
the adsorption capacity of heavy metal ions/dyes can be improved. It is
observed from previous studies that conducting copolymers based on
PANI can be used effectively for the removal of some toxic metal ions
from aqueous solutions.
Lu et al. easily synthesized poly(aniline-co-m-sulfophenylene-dia-
mine) (PANICSP) nanoparticles by an oxidative precipitation poly-
merization of aniline (AN) and m-sulfophenylene-diamine (SP) in HCl
without any external stabilizer. They studied the adsorption of Pb(II)
and Hg(II) ions by the HCl-doped PANICSP copolymer considering
different Ani/SP ratios. It was shown that the PANICSP nanoparticles
with the AN/SP (70:30) ratio had the highest Hg(II) adsorbance and
adsorptivity of 497.7 mg/g and 98.8%, respectively (Lü et al., 2007). It
was proposed that the Pb(II) and Hg(II) adsorption could be responsible
for a complexation between Pb(II) or Hg(II) ions and the nitrogen atoms
of the -N˭C- groups through sharing their four lone pairs of electrons
(Lü et al., 2007).
Li et al. introduced poly (aniline-co-5-sulfo-2-anisidine) (PANICSA)
nanoparticles, synthesized by chemical oxidative co-polymerization of
Ani and 5-sulfo-2-anisidine (5S2A) monomers, as adsorbent for the
strong adsorption of Hg(II) ions from aqueous solution. The maximum
Hg(II) sorption capacity on the particulate nano-sorbents was reported
to be 2063 mg/g (Li et al., 2009a, 2009b).
In another study, Li et al. presented poly(aniline-co-1,8-diamino-
naphthalene) (PANDAN) copolymer fabricated by chemical oxidation
co-polymerization as adsorbent for the selective removal of Cr(VI) ions.
It was reported that the PANDAN copolymer had the preferable ad-
sorption with the maximum capacity 154.7 mg/g toward Cr(VI) in the
presence of K(I), Ca(II), Mg(II) and H2PO4− at pH 4. It was proposed
Fig. 4. A possible growth route of PmPD-M100 nanorods syn-
thesized in MeOH media (Su et al., 2013).
E.N. Zare et al. Environmental Research 162 (2018) 173–195

Fig. 5. SEM images of the synthesized PoPDA (A, B and C) and PpPDA (G, H and I) and TEM images of the synthesized PmPDA (D, E and F) by various methods (Archana and Jaya
Shanthi, 2015; Dai et al., 2015; Han et al., 2011; Meng et al., 2014; Min et al., 2011; Su et al., 2013; Wang and Liao, 2012).

that Cr(VI) be removed from aqueous solutions through an adsorption-
coupled reduction process, in which the PANDAN provides protons for
the reduction of Cr(VI) to Cr(III) (X. Li et al., 2015).
Bhaumik et al. used poly(pyrrole-co-aniline) (PPy-PANI) nanofibers
fabricated via the polymerization of Py and Ani monomers in the pre-
sence of FeCl3 oxidant for the removal of Cr(VI) from aqueous solution.
The effect of pH, the dose of adsorbent, contact time, concentration of
Cr(VI) and temperature were investigated and the obtained results
showed that the maximum adsorption capacity for Cr(VI) by the PPy-
PANI nanofibers was 227 mg/g at pH 2, adsorbent dose of 50 mg,
contact time of 400 min, Cr(VI) centration of 100 ppm and temperature
of 25 °C (Bhaumik et al., 2012).
Huang et al. introduced strong heavy metal ion sorbents based on
copolymer microparticles with many functional groups including
amino, imino and sulfonic groups synthesized by a chemical oxidative
polymerization of m-phenylenediamine (mPDA) and p-sulfonic-m-
phenylenediamine (SPD) in pure water. The mPDA/SPD (95/5) copo-
lymer microparticles demonstrated maximum yield, electrical con-
ductivity, and Pb(II) and Cr(VI) (mainly as HCrO4-) adsorbability, but
minimum Cu(II) adsorbability. However, the mPD/SPD (50/50) copo-
lymer microparticles demonstrated maximum Hg(II) adsorbability. It
was also exhibited that the microparticles had good selective ad-
sorptivity of up to 99.9% for Hg(II) and Pb(II) (Huang et al., 2012).
Zare et al. developed novel poly(aniline-co-m-phenylenediamine)
(PAMpDA) and poly(aniline-co-3-aminobenzoic acid) (PA3ABA) copo-
lymers nanoparticles synthesized through copolymerization approach
for the removal of Cd(II), Co(II) and Pb(II) from aqueous solutions.
They investigated the effect of pH, adsorption dosage, contact time, and
initial concentration of metal ions. The maximum adsorption percen-
tages for Cd(II), Co(II), and Pb(II) were determined to be 85%, 90%,

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Table 7
Data on the sorption of heavy metal ions/dyes by PANI.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PoPDA microspheres Ag(I) 5 30 533 99.1 (Li et al., 2009)

PoPDA microspheres Hg(II) 1-9 30 394 96.7 (Li et al., 2009)
PoPDA microspheres Cr(VI) below 4 24 98.23 99.04 (Wang and Liao, 2012)
PoPDA hollow microspheres Pb(II) 6 30 103.20 above 90 (Han et al., 2011)
PoPDA hollow microspheres Cd(II), Cu(II) 6 30 N.R above 60 (Han et al., 2011)
PmPDA microparticles Pb(II) 2.5–4.2 30 242.7 above 95 (Huang et al., 2006)
PmPDA microparticles Hg(II) 4 25 955 97.83 (Tang et al., 2011)
PmPDA microparticles SO3-2 1.75 25 487.95 95 (Sang et al., 2013)
Cu–PmPDA microparticles MB Acidic 25 96.1 N.R (Yu et al., 2013a)
PmPDA microparticles Cr(VI) 2 30 500 Above 99 (Yu et al., 2013b; Yu et al., 2013c)
PmPDA nanorods Ag(I) 6 30 2073 N.R (Su et al., 2013)
PmPDA hollow nanostructure Ag(I) 6 30 2359.3 N.R (Su et al., 2014)
PmPDA nanoparticles Ag(I) 6 30 1767 N.R (Yu et al., 2013a)
Hollow Cu-PmPDA particles As(V) 5.2 35 27.4 99.99 (Dai et al., 2015)
PmPDA nanobelts OG N.R 30 460 N.R (Meng et al., 2014)
PpPDA microspheres Pb(II) 2.5–4.2 30 253.2 above 97 (Huang et al., 2006)
PpPDA microspheres Cr(VI) 1 25 N.R 79.13 (Archana and Jaya Shanthi, 2015)
PpPDA microspheres Pb(II) N.R 25 above 1800 99.8 (Min et al., 2011)

2012; Karthik and Meenakshi, 2015a; Lü et al., 2007; Zare et al., 2016,
2015b). Table 8 displays data on the sorption of heavy metal ions/dyes
by PANI copolymers. Accordingly, the PANI copolymers with more
effective pendant groups, such as amine, carboxyl and hydroxyl groups
result in the enhancement of pollutants removal.

2.2. Nanocomposites based on polyaniline and its derivatives

Other functional materials, such as natural polymers, agricultural

Fig. 6. The uptake mechanism of Pb(II) from water by PA3ABA (Zare et al., 2016).
and 80% at pH 6, adsorption dosage of 50 mg, contact time of 70 min,
and initial concentration of 50 ppm. A mechanism based on the che-
lating effect between NH2/COO- groups and Pb(II) ions was also sug-
gested (Fig. 6) (Zare et al., 2016). They expressed that amine and
carboxyl groups in the main chain structure of copolymer were com-
plexed to Pb(II) ions.
Karthik et al. employed PANI grafted CS (PANIGCS) as an adsorbent
for the removal of Pb(II) and Cd(II) ions from aqueous solution. It was
reported that in the presence of other common metal ions, the ad-
sorption of Pb(II) and Cd(II) ions onto the PANIGCS was negatively
influenced and the maximum monolayer capacity was 16.07 and
14.33 mg/g for Pb(II) and Cd(II) ions, respectively. They showed that
the sorption capacity of PANIGCS increased with the increase of pH,
which was mainly due to both ion exchange and electrostatic attraction
followed by complexation between the metal ions and PANIGCS
(Karthik and Meenakshi, 2015a). A mechanism for the adsorption of Pb
(II) and Cd(II) ions onto the PANIGCS was proposed (Fig. 7) (Karthik
and Meenakshi, 2015a). Fig. 7 shows that the removal of Pb(II) and Cd
(II) ions was highly pH dependent. The maximum removal was at pH 6,
in which the PGC acquired negatively charged surface enhancing its
electrostatic attraction with the metal ions followed by complexation.
Igberase et al. prepared chitosan beads from chitosan flakes grafted
with PANI to enhance the adsorption properties of chitosan-based
material for Cu(II) ions. The effects of pH, contact time and initial
concentration in a batch system were investigated and the results
showed that the maximum adsorption capacity for Cu(II) ions was
100 mg/g at pH 5–6 with a contact time of 180 min, and initial con-
centration of 40 ppm (Igberase et al., 2014). Fig. 8 shows the SEM
images of various PANI copolymers (Bhaumik et al., 2012; Huang et al.,
residues, inorganic materials, and organic molecules are combined with
PANI and its derivatives to produce PANI-based nanocomposites to
enhance its surface area and change its surface morphology. Depending
on the nature of the incorporating functional materials, the PANI-based
nanocomposites can be discussed as PANI and its derivatives/natural
materials nanocomposites, PANI and its derivatives/organic material
nanocomposites and PANI and its derivatives/inorganic material na-
nocomposites.
2.2.1. PANI and its derivatives/natural materials nanocomposites
Adsorption of different heavy metal ions/dyes by various nano-
composites based on PANI and its derivatives with natural materials is a
very promising process in terms of low cost, renewable and sustainable
sources. The main benefit of this type of bio-nanoadsorbent is its
massive range of effectiveness. Several forms of inexpensive materials,
such as starch, dextrin, chitosan, rice husks, sawdust, etc. have been
studied as potential bio-adsorbents for the removal of heavy metal ions/
dyes.
2.2.1.1. PANI/Sawdust (PANI/SD) nanocomposites. Sawdust (SD),
obtained from wood industry, is a plentiful byproduct, inexpensive
and easily available. SD could easily coat with PANI nanoparticles
(50–100 nm) and form PANI/SD nanocomposites which can be bound
to heavy metal ions/dyes via different conditions and mechanisms.
Numerous studies on the effectiveness of PANI/SD nanocomposites for
the removal of heavy metal ions/dyes were introduced by some
researchers (Ansari and Mosayebzadeh, 2010a, 2010c; Ansari and
Raofie, 2006; Ansari, 2006; Mansour et al., 2011).
Ansari et al. showed that PANI/SD nanocomposites have consider-
able potential for EY, MO, Cr(VI), and Pb(II) removal from aqueous
solution. The optimum conditions of sorption were at PANI/SD dose of
0.1–0.8 g, contact time of 40–120 min, pH 2–6 and temperature of
25 °C. The removal percentages of EY, MO, Cr(VI), and Pb(II) in the
optimum conditions were 96%, 89%, 100%, and 98%, respectively
(Ansari and Mosayebzadeh, 2010a, 2010c; Ansari and Raofie, 2006;
Ansari, 2006).

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Mansour et al. investigated the ability of PANI coated on sawdust as
nanocomposite adsorbent for the adsorptive removal of Cd (II) ions
from aqueous solutions. Various physico-chemical parameters, such as
pH, initial metal ion concentration, adsorbent dosage level, and equi-
librium contact time were studied. The maximum adsorption capacity
of 430 mg/g for Cd(II) on the PANI/SD nanocomposite was determined
to be at pH 6, initial metal ion concentration of 40 ppm, adsorbent
dosage level of 0.75 g and equilibrium contact time of 20 min (Mansour
et al., 2011).
2.2.1.2. PANI/ Rice husk ash (PANI/RHA) nanocomposites. Rice husk is
a natural abundant by-product generally obtained from rice crush. Rice
husk ash (RHA) is a solid obtained after the burning of rice husk
(Ghorbani and Eisazadeh, 2013). PANI/RHA nanocomposite was
prepared by coating the RHA substrate with Ani by the chemical
oxidative polymerization. A few researchers reported the PANI/RHA
nanocomposite as an adsorbent for the removal of heavy metal ions/
dyes from wastewater.
Ghorbani et al. synthesized the PANI/RHA nanocomposites with the
diameter of about 50–100 nm via cast method for the removal of che-
mical oxygen demand (COD), dyes, anions, Cd(II), and Cu(II) from
cotton textile wastewater (Ghorbani and Eisazadeh, 2013). They pro-
posed an adsorption mechanism for the complexation between anions
or heavy metal ions and the nitrogen atoms of the -N˭C- groups through
sharing their lone pair of electrons (Fig. 9). Also, they employed the
PANI/RHA nanocomposites for Hg(II) and Zn(II) removal from aqueous
solution. They studied the influence of various experimental parameters
such as, pH, adsorbent dosage, contact time and rotating speed. The
removal percentages of 95% for Hg(II) and 85% for Zn(II) were re-
ported at optimum conditions including pH 3–9, adsorbent dosage of
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Fig. 7. Proposed mechanism for the adsorption of Pb(II) and Cd
(II) ions onto the PANIGCS (Karthik and Meenakshi, 2015a).
10 g/L, equilibrium contact time of 20 min and rotating speed of
400 rpm (Ghorbani, 2012; Ghorbani et al., 2011). Fig. 10 displays the
SEM and TEM images of PANI/RHA nanocomposite (Ghorbani and
Eisazadeh, 2013; Ghorbani et al., 2011).
2.2.1.3. PANI and its derivatives/polysaccharide nanocomposites. In the
last decades, there has been significant interest in the synthesis of PANI
and its derivatives/polysaccharide nanocomposite that include
different chemical and biological polymers. This develops an
important area of composite research because of its application in
material science and environmental sciences. The only Janaki et al.
synthesized the eco-friendly polyaniline/chitosan (PANI/CS)
nanocomposite, with the diameter of about 50–100 nm, as an
adsorbent to remove CR, CBB, RBBR, and MB from aqueous solution.
It was shown that the surface of the composite was rough with pleats,
providing a good possibility for dye adsorption. The maximum removal
percentages at the contact time of 60 min, initial dye concentration of
100 mg/L, pH 3, and adsorbent dose of 0.1 g/L were found to be 95.4%,
98.2%, and 99.8% for CR, CBB, and RBBR, respectively. It was also
reported that the amino and hydroxyl groups on the PANI/CS were the
main functional groups involved in the adsorption of dyes (Janaki et al.,
2012a).
In another study, Janaki et al. evaluated the PANI/starch nano-
composite, with the diameter of about 70–90 nm, synthesized by the
chemical oxidative polymerization of Ani in the presence of starch for
the removal of RB5 and RV4 dyes from aqueous solutions. It was re-
ported that the PANI/starch nanocomposite could significantly remove
RB5 (99%) and RV4 (98%) from aqueous solutions at pH 3. The hy-
drogen bonding and electrostatic interactions between nanocomposite
and dyes were responsible for the enhanced adsorption (Janaki et al.,
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Fig. 8. SEM images of the PANICSP nanoparticles (A), PPy-PANI nanofibers (B), PmPDACSPD microparticles (C), PAMpDA nanoparticles (D), PA3ABA nanoparticles (E) and PANIGCS (F)
(Bhaumik et al., 2012; Huang et al., 2012; Karthik and Meenakshi, 2015a; Lü et al., 2007; Zare et al., 2016, 2015b).

Table 8
The data on the sorption of heavy metal ions/dyes by PANI copolymers.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PANICSP nanoparticles Hg(II) N.R 30 497.7 98.8 (Lü et al., 2007)

PANICSA nanoparticles Hg(II) 2.51–2.98 30 2063 100 (Li et al., 2009a, 2009b)
PANDAN Cr(VI) 4 25 154.7 Above 95 (J. Li et al., 2015; S. Li et al., 2015; X. Li et al., 2015; K. Li et al., 2015)
PPy-PANI nanofibers Cr(VI) 2 25 227 99.83 (Bhaumik et al., 2012)
PmPDACSPD microparticles Pb(II) 2.70 30 91.8 91.8 (Huang et al., 2012)
Hg(II) 2.24 549 90
Cr(VI) 4.65 226 98
PAMpDA nanoparticles Cd(II) 6 25 N.R 90 (Zare et al., 2015b)
Co(II) 6 25 86.20 92
Pb(II) 6 25 N.R 82
PA3ABA nanoparticles Pb(II) 6 25 81.43 80 (Zare et al., 2016)
PANIGCS Pb(II) 6 25 13.23 98.21 (Karthik and Meenakshi, 2015a)
Cd(II) 6 25 12.87 94.92
PANIGCS Cn(II) 5 45 100 100 (Igberase et al., 2014)

2012c).
In a study, Zare et al. used biodegradable PANI/dextrin (PANI/Dex)
nanocomposite, with the diameter of about 70–80 nm, as a sorbent for
the removal of Cu(II), Pb(II) and Cd(II) ions. They presented that the
removal percentages at the optimum conditions including nano-
composite dosage of 1 g/L, heavy metal ions concentration of 100 ppm,
contact time of 120 min, and pH 3–6 were 52%, 48%, 26% for Cu(II),
Pb(II), and Cd(II) ions, respectively. The low adsorption of these metal
cations on the studied nanocomposite was reported due to the proto-
nation of active sites in the PANI-Dex (Zare and Lakouraj, 2014).
Janaki et al. reported PANI/extracellular polymeric substances
(PANI/EPS) as an adsorbent for the removal of RBBR, RO16 and
Remazol dyes. The maximum removal percentages were 99%, 98%, and
99.8% for RBBR, RO, and Remazol, respectively. Also, the electrostatic
interactions between the dye and the nitrogen present in the polymer
identified as a major mechanism in the adsorption process (Janaki
et al., 2012b, 2012d).
Debnath et al. introduced PANI/lignocellulose (PANI/LC) nano-
composite, with the diameter of about 500–1000 nm, as an adsorbent
for the removal of CR from aqueous solutions. It was reported that the
combined effect of pH and initial dye concentration was antagonistic;
the combined effect of initial dye concentration and temperature was
synergistic, while the combined effect of pH and temperature was re-
ciprocal. Also, the maximum CR adsorption capacity on PANI/LC was
found to be 1672.5 mg/g at pH 4.29, initial dye concentration of
28.5 mg/L, and adsorbent dosage of 0.69 g/L (Debnath et al., 2015).

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Jiang et al. assembled PANI nanofiber micro- or millimeter-scale
calcium alginate (CA) (PANI/CA) beads by the “competitive adsorption-
restricted polymerization” method for the removal of Cu(II) and Pb(II)
ions. The removal percentage was 90% for Cu(II) and Pb(II) ions in a
wide pH range from 3 to 7 (Jiang et al., 2012).
Yavuz et al. studied the effect of substituted aniline, (N-methylani-
line) (NMANI), N-ethylaniline (NEANI) and 2-ethylaniline (2 EANI) on
the adsorption efficiency by synthesizing some poly(alkyl-substituted
aniline)/chitosan composites with the diameter of about 300–500 nm
and the results showed that PNEANI/chitosan (PNEANI/CS) nano-
composite had the highest removal ability for Cr(VI) (229.8 mg/g)
(Yavuz et al., 2011).
Abdelwahab et al. fabricated the poly(p-phenylenediamine)/chit-
osan (PpPDA/CS) composite, with the diameter of about 500–1000 nm,
by in-situ chemical oxidative polymerization of pPDA into CS using
ammonium APS, as an oxidant, for the removal of Cu(II) ions from
aqueous solutions. The maximum adsorption capacity of 650 mg/g for
Cu(II) was seen at pH 6 and contact time of 360 min (Abdelwahab et al.,
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Fig. 9. Possible complexations and ion exchanges between anions
or heavy metal ions and –NH- groups on the PANI/RHA nano-
composite chains (Ghorbani and Eisazadeh, 2013).
Fig. 10. SEM and TEM images of PANI/RHA nano-
composite (Ghorbani and Eisazadeh, 2013; Ghorbani
et al., 2011).
2015). Table 9 reports the data on the sorption of heavy metal ions/
dyes by PANI and its derivatives/natural materials nanocomposites.
Accordingly, the maximum removal percentage is related to the PANI/
SD (100% for Cr(VI)) and PANI/LC (99.85% for CR).
2.2.2. PANI and its derivatives/synthetic polymers nanocomposites
Polyethylene glycol (PEG), polystyrene (PS), polyamide (PAM),
polyvinyl alcohol (PVA) and poly(ethylene terephthalate) (PET) mate-
rials have been fabricated with PANI and extensively applied in was-
tewater purification.
Gupta et al. and Lashkenari et al. investigated the ability of poly-
aniline/polystyrene (PANI/PS) nanocomposite fabricated via solution
mixing and microemulsion polymerization as high performance syn-
thetic adsorbent for the adsorptive removal of Hg(II) and Cr(VI) ions
from aqueous solutions. The maximum removal percentage of 67.1%
and the maximum adsorption capacity of 19 mg/g were reported for Hg
(II) and Cr(VI) ions, respectively. The optimum conditions for Hg(II)
and Cr(VI) removal were determined at pH 4–4.2, adsorbent dosage of
E.N. Zare et al. Environmental Research 162 (2018) 173–195

Table 9
The data on the sorption of heavy metal ions/dyes by PANI and its derivatives/natural materials nanocomposites.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PANI/SD Cr(VI) 1–2 25 N.R 100 (Ansari, 2006)

PANI/SD EY 2 25 5.90 99.60 (Ansari and Mosayebzadeh, 2010a)
PANI/SD MO 6 25 1.37 89 (Ansari and Mosayebzadeh, 2010c)
PANI/SD Pb(II) 6 25 N.R 98.2 (Ansari and Raofie, 2006)
PANI/SD Cd(II) 5 25 430 N.R (Mansour et al., 2011)
PANI/RHA COD N.R 25 N.R 92.5 (Ghorbani and Eisazadeh, 2013)
Color N.R 25 N.R 87.95
Cl- N.R 25 N.R 83.3
SO3−2 N.R 25 N.R 82.83
Cu(II) N.R 25 N.R 89.02
Cd(II) N.R 25 N.R 89.63
PANI/RHA Hg(II) 9 25 N.R 95 (Ghorbani et al., 2011)
PANI/RHA Zn(II) 3 25 24.3 85 (Ghorbani, 2012)
PANI/CS CR 3 25 322.58 95.4 (Janaki et al., 2012a)
CBB 3 25 357.14 98.2
RBBR 3 25 303.03 99.8
PANI/St RB 3 25 0.81 99 (Janaki et al., 2012c)
RV 3 25 0.83 98
PANI/Dex Cu(II) 3 25 N.R 52 (Zare and Lakouraj, 2014)
Pb(II) 3 25 N.R 48
Cd(II) 3 25 N.R 26
PANI/EPS RBBR 3 30 0.5775 99 (Janaki et al., 2012d)
RO 3 40 0.4748 98
PANI/EPS Remazol 3 25 N.R 99.8 (Janaki et al., 2012b)
PANI/LC CR 4.29 25 1672.5 99.85 (Debnath et al., 2015)
PANI/CA Cu(II) 3–7 25 67.95 90 (Jiang et al., 2012)
Pb(II) 3–7 25 251.25 90
PNEANI/CS Cr(VI) 4.2 25 229.8 90 (Yavuz et al., 2011)
PpPDA/CS Cu(II) 6 30 650 84.38 (Abdelwahab et al., 2015)

0.1–15 g/L, and equilibrium time of 30–40 min (Gupta et al., 2004;
Lashkenari et al., 2012).
Samani et al. fabricated the PANI/PEG nanocomposite through the
polymerization of Ani in the presence of PEG as an adsorbent for the
removal of Cr(VI) ions. They showed that the maximum removal of Cr
(VI) ions was above 90% at an agitation time of 30 min, pH 5, PANI/
PEG dose of 1 g/L and initial concentration of chromium salt 50 ppm.
They also reported that the removal mechanism of chromium by PANI/
PEG was a combination of surface adsorption and reduction reaction
(Samani et al., 2010).
Xia et al. used polyamide 6/ PANI (PAM/PANI) core-shell nano-
composite fiber synthesized via an in-situ oxidation polymerization
technique for MO dye removal. It was displayed that the cam-
phorsulfonic acid played an important role for the formation of core-
shell nanocomposite structure. The maximum adsorption capacity of
MO dye was reported as 81.9 mg/g at 40 °C (Xia et al., 2013).
Karthik et al. described the synthesis of PANI/polyvinyl alcohol
(PANI/PVA) nanocomposite by an in-situ polymerization method as an
adsorbent for Cr(VI) ions removal. They demonstrated that the high
adsorption of Cr(VI) ions with the maximum sorption capacity of
111.23 mg accomplished at pH 4.12 with the Cr(VI) initial concentra-
tion of 200 mg/L (Karthik and Meenakshi, 2015b).
Najim et al. employed PANI/ poly(ethylene terephthalate) (PANI/
PET) nanocomposite prepared via in-situ oxidative polymerization of
Ani in acidic medium using ammonium persulfate (APS), as an initiator,
in the presence of PET powder for the removal of Cr(VI) ions from
aqueous solutions. The removal percentage was 95.21% for Cr(VI) ions
at pH 2. They also reported that the potential in the removal of chro-
mium by PANI/PET nanocomposite was due to the large surface area of
PANI/PET nanocomposite (Najim and Salim, 2014).
Unfortunately, up to date reporting, there have been no reports on
the use of a PANI derivatives/synthetic polymers nanocomposite as an
adsorbent for the removal of pollutants from water. Fig. 11 displays
SEM images of PANI/St nanocomposite (A), PANI/Dex nanocomposite
(B), PANI/CA nanocomposite (C), PANI/PS nanocomposite (D), PANI/
PVA nanocomposite (E) and PANI/PET nanocomposite (F) (Janaki
et al., 2012c; Jiang et al., 2012; Karthik and Meenakshi, 2015b;
Lashkenari et al., 2012; Najim and Salim, 2014; Zare and Lakouraj,
2014). According to Fig. 11, the presence of CA and PS results in the
establishment of homogeneous structures. Table 10 shows data on the
sorption of heavy metal ions/dyes by PANI derivatives/synthetic
polymers nanocomposite.
2.2.3. PANI and its derivatives/inorganic material nanocomposites
The synthesis of polymer/inorganic material nanocomposites has
potential applications in industries and has attracted much attention in
water purification recently. In this regard, the use of nanocomposites
based on PANI and its derivatives with various inorganic nanoparticles
has proven to be promising for the high adsorption of heavy metal ions/
dyes. Many researchers developed the use of PANI and its derivatives
/inorganic nanocomposites for the removal of heavy metal ions/dyes
from water.
2.2.3.1. PANI and its derivatives/iron/iron oxide nanocomposites. The use
of magnetic nanocomposites in water purification is promising due to
high efficiency, simplicity of operation and cost effectiveness. Magnetic
separation, in comparison with other techniques, such as precipitation,
centrifugation and filtration has revealed facile operation and reduced
capital costs (Lakouraj et al., 2014a, 2014b; Zare et al., 2016).
Consequently, composite systems with magnetic nanoparticles have
been extensively used in the adsorption processes to improve the
separation step after water treatment. Magnetic adsorbents are
usually composed of the magnetic cores to ensure a strong magnetic
response and a polymeric shell to supply favorable functional groups for
various applications (Lakouraj et al., 2014a, 2014b; Zare et al., 2016).
Recently, some nanocomposites consisting of different types of PANI
and its derivatives or its co-polymers containing iron or iron oxide
nanoparticles have been reported as adsorbents for the removal of
pollutants, such as Humic acid, MB, MG, CR, anions, Pb(II), Cd(II), As
(V), Cr(III), Cr(VI), Co(II), and Cu(II) ions from water (Bhaumik et al.,
2014; Ghorbani et al., 2010; Lakouraj et al., 2015; Li et al., 2013a;
Norouzian and Lakouraj, 2015b; Tang et al., 2014; Tian et al., 2015;

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Fig. 11. SEM images of PANI/St nanocomposite (A), PANI/Dex nanocomposite (B), PANI/CA nanocomposite (C), PANI/PS nanocomposite (D), PANI/PVA nanocomposite (E) and PANI/
PET nanocomposite (F) (Janaki et al., 2012c; Jiang et al., 2012; Karthik and Meenakshi, 2015b; Lashkenari et al., 2012; Najim and Salim, 2014; Zare and Lakouraj, 2014).

Table 10
The data on the sorption of heavy metal ions/dyes by PANI derivatives/synthetic polymers nanocomposite.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PANI/PS Hg(II) 4.12 30 N.R 67.1 (Gupta et al., 2004)

PANI/PS Cr(VI) 4 30 19 73.26 (Lashkenari et al., 2012)
PANI/PEG Cr(VI) 5 25 109.9 90 (Samani et al., 2010)
PAM/PANI MO Basic 40 81.9 85 (Xia et al., 2013)
PANI/PVA Cr(VI) 4 50 111.23 95 (Karthik and Meenakshi, 2015b)
PANI/PET Cr(VI) 2 25 3.02 95.21 (Najim and Salim, 2014)

Wang et al., 2014a, 2014b). The in-situ polymerization and/or the
copolymerization approaches were used for the fabrication of magnetic
nanocomposite based on PANI and its derivatives or co-polymers. It was
reported that the incorporation of magnetic nanoparticles into PANI
and its derivatives can result in the increase of surface-to-volume ratio,
which improves the sorption capacity of magnetic nanocomposite re-
lative to bare PANI and its derivatives or co-polymers. It was proposed
that the presence of amine-functionalized groups on the PANI and its
derivatives or co-polymers’ backbone, together with the iron or iron
oxide nanoparticles, may result in the formation of heavy metal ions/
dye complexes through the chelation or metal/dye exchange in the
adsorbents. The magnetic nanocomposites based on PANI derivatives
and its copolymers showed higher adsorption capacities than those
based on PANI. This fact can be attributed to the presence of many
pendant functional groups, such as COOH and NH2, as active sites in the
repeating unit of polymers and copolymers, which increase the com-
plexation process for metal and dye removal.
Wang et al. and Liu et al. prepared magnetic PmPDA/Fe3O4 and
Laccase (Lac) immobilized PpPDA/Fe3O4 (Lac/ PpPDA/Fe3O4) nano-
composites via the directly coating method, the immobilization of Lac
onto PpPDA/Fe3O4 for Cr(VI), and RB 19 removal from aqueous solu-
tions, respectively. The maximum adsorption capacity and removal
efficiency were reported as 246.09 mg/g for Cr(VI) and 80% for RB 19
(Liu et al., 2016; Wang et al., 2015).
Zare et al designed the poly(aniline-co-m-phenylenediamine)/Fe3O4
(PAMpDA) and poly(aniline-co-3-aminobenzoicacid)/Fe3O4 (PA3ABA@
Fe3O4) nanocomposites fabricated through in-situ co-precipitation and co-
polymerization techniques for the removal of Co(II), and Pb(II) ions from
aqueous solutions, respectively. The maximum reported adsorption capa-
cities were 116.27 and 138.31 mg/g for Co(II) and Pb(II) ions, respectively,
which were much higher than those of the magnetic nanocomposites based
on PANI (Zare et al., 2016, 2015b). Table 11 shows the data on the sorption
of heavy metal ions/dyes by PANI and its derivatives/iron/iron oxide na-
nocomposites.
2.2.3.2. PANI/silica nanocomposite. Silica crystalline has a large
specific surface area, moderate cation exchange capacity and
reactive-OH groups on its surface, which can adsorb and trap heavy
metal ions/dyes from wastewater (Wang et al., 2011). To reduce costs
and improve the comprehensive water-absorbing properties of the
material, fabricating a nanocomposite composed of polymer and silica
crystalline materials was considered a priority. Different silica
crystalline forms including attapulgite, clinoptilolite, silica gel,
hexagonal mesoporous silica, bentonite and zeolite were used to
fabricate unique PANI/silica nanocomposites for water treatment.
Many researchers have used PANI/silica nanocomposites as
adsorbents for the removal of humic acid, Cu(II), Ni(II), Cd(II), Cr
(VI), MB, Hg(II), Ni(II), Mo(VI), W(VI), and V(V) from wastewater
(Ayad et al., 2012; Cui et al., 2012; Gupta et al., 2014; Javadian et al.,
2014, 2013; Karthik and Meenakshi, 2014; Kong et al., 2011; J. Li et al.,

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Table 11
The data on the sorption of heavy metal ions/dyes by PANI and its derivatives/iron/iron oxide nanocomposites.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PANI/Fe3O4 SO3−2 N.R 25 N.R 75 (Ghorbani et al., 2010)

Cl- N.R 25 N.R 75
Cu(II) N.R 25 N.R 62
Fe(II) N.R 25 N.R 65
PANI/Fe3O4 Cr(VI) 2–3 25 N.R Above 99 (Li et al., 2013a)
PANI/Fe As(V), 7 25 42.37 N.R (Bhaumik et al., 2014)
Cr(VI) 2 25 434.78 N.R
CR 7.5 25 243.9 N.R
PANI/Fe3O4/SiO2 Humic acid 2 25 36.36 N.R (Wang et al., 2014)
PANI/MMS Cr(VI) 2 25 193.85 95 (Tang et al., 2014)
Fe3O4@PAmA-BAmPD-TCATS MB 8 25 31.64 83.15 (Lakouraj et al., 2015)
MG 8 25 29.06 92.45
PANI/TCAS Cr(III) 8 25 833.3 92.5 (Norouzian and Lakouraj, 2015b)
Cu(II) 8 25 555.5 99.9
Co(II) 8 25 562.3 99.5
Cd(II) 8 25 500 99
PmPD/Fe3O4/MWCNT Cr(VI) 2 25 346 N.R (Tian et al., 2015)
PmPDA/Fe3O4 Cr(VI) 2 30 246.09 N.R (Wang et al., 2015)
Lac/ PpPDA/Fe3O4 RB19 3.5 65 N.R 80 (Liu et al., 2016)
PAMpDA/Fe3O4 Co(II) 6 25 116.27 92 (Zare et al., 2015b)
PA3ABA/Fe3O4 Pb(II) 6 25 138.31 89 (Zare et al., 2016)

Fig. 12. TEM images of PANI/Attapulgite (A), PANI/HMS (B) and PANI/ZSP (C) nanocomposites (Javadian et al., 2013; R. Kumar et al., 2013; K.Y. Kumar et al., 2013; Wang et al., 2011).

Table 12
The data on the sorption of heavy metal ions/dyes by PANI/silica nanocomposites.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PANI/Attapulgite Humic acid 5 35 61.35 N.R (Wang et al., 2011)

PANI/ Attapulgite Cu(II) 3 25 114 N.R (Kong et al., 2011)
Ni(II) 3 25 84 N.R
Cd(II) 3 25 56 N.R
Cr(VI) 5 25 198 N.R
PANI/Clinoptilolite Cr(VI), 7 25 N.R 98 (Olad et al., 2011)
PANINTs/Silica MB N.R 25 10.31 N.R (Ayad et al., 2012)
PANI/Attapulgite Hg(II) 5-9 25 800 N.R (Cui et al., 2012)
PANI/HMS Ni(II) >8 35 17.92 99.87 (Javadian et al., 2013)
PANI/NS Cr(VI), 2 25 4.94 95.20 (Najim and Salim, 2014)
PANI/Silica gel Cr(VI), 4.2 30 63.41 100 (Karthik and Meenakshi, 2014)
PANI/HMS Hg (II) 10 25 843 100 (Javadian et al., 2014)
PANI/Zeolite Cr(VI), 2 25 22 100 (Shyaa et al., 2015)
PANI/Attapulgite Pb(II) N.R 25 15.42 66.5 (S. Li et al., 2015)
PANI/Bentonite Cr(VI), Mo(VI), W(VI), V(V) 1.7 25 0.188 99.99 (Ryabchenko et al., 2016)
7 25 0.066 49.32
1-9.2 25 2.080 99.99
8 25 0.031 49.40
PANI/ZSP MB 1 25 12 Above 91 (Gupta et al., 2014)

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2015; S. Li et al., 2015; X. Li et al., 2015; K. Li et al., 2015; Najim and
Salim, 2014; Olad et al., 2011; Ryabchenko et al., 2016; Shyaa et al.,
2015; Wang et al., 2011). Several factors, affecting the adsorption
capacity, including temperature, pH, contact time, adsorbent dosage,
and initial concentration of metal ions/dyes were investigated. The
maximum adsorption value in the range of 25–843 mg/g was found at
pH 2–10 and a temperature of 25–40 °C (Ayad et al., 2012; Cui et al.,
2012; Gupta et al., 2014; Javadian et al., 2014, 2013; Karthik and
Meenakshi, 2014; Kong et al., 2011; S. Li et al., 2015; Najim and Salim,
2014; Olad et al., 2011; Ryabchenko et al., 2016; Shyaa et al., 2015;
Wang et al., 2011). To the best of our knowledge, no studies on the use
of PANI derivatives/silica nanocomposite as an adsorbent for the
removal of heavy metal ions/dyes from an aqueous solution have
been reported to date. Fig. 12 shows TEM images of PANI/Attapulgite
(A), PANI/HMS (B) and PANI/ZSP (C) nanocomposites (Javadian et al.,
2013; R. Kumar et al., 2013; K.Y. Kumar et al., 2013; Wang et al.,
2011). Table 12 displays the data on the sorption of heavy metal ions/
dyes by PANI/silica nanocomposites.
2.2.3.3. PANI/other inorganic nanoparticles composites. Various inorganic
nanoparticles, such as MWCNTs, graphene/graphene oxide, zirconium
oxide, zirconium phosphate, Mn2O3, tungstomolybdophosphate, carbon
active, Mg/Al and Sb2O3 were also used for the preparation of
nanocomposites based on PANI as adsorbent for water purification
(Agarwal et al., 2016; Gopal et al., 2014; Khalili and Eisazadeh, 2013;
R. Kumar et al., 2013; K.Y. Kumar et al., 2013; Li et al., 2013b;
Rajakumar et al., 2013; Wang et al., 2012; Zhu et al., 2016).
Kumar et al. introduced PANI/ MWCNTs nanocomposite synthe-
sized by in-situ oxidative polymerization as an effective adsorbent for
the removal of Cr(VI) from water. The maximum adsorption capacity
was 55.5 mg/g at the optimum conditions including pH 2, metal ion
concentration 100 ppm, adsorbent dose 0.02 g, temperature 30 °C, and
contact time 6 h. The functional groups, mainly amine or imine groups,
present on the surface of the adsorbent and the internal porous sites
were reported to be responsible for the adsorption of Cr(VI) (R. Kumar
et al., 2013; K.Y. Kumar et al., 2013).
Li et al. synthesized the PANI/reduced grapheme oxide (PANI/RGO)
nanocomposite via polymerization of Ani in the presence of GO, and
further reduction by hydrate hydrazine as an effective adsorbent to-
wards the adsorption of Hg(II) in aqueous solutions. The maximum
adsorption capacity of PANI/RGO nanocomposite for Hg(II) was
1000 mg/g at pH 4.0 (Li et al., 2013b).
Wang et al. utilized the PANI/α-zirconium Phosphate (PANI/ α-ZrP)
nanocomposite fabricated via in-situ oxidative polymerization for the
adsorption of MO dye from aqueous solutions. It was exhibited that the
PANI/α-ZrP nanocomposite had excellent maximum adsorption capa-
city toward MO (377.46 mg/g), which was superior to that of PANI
nanotubes (254.15 mg/g) and much higher than that of many other
adsorbents. The MO adsorption decreased with increasing solution pH
at pH > 4.0, which can be due to the electrostatic interactions between
amine and imine groups on the surface of PANI/α -ZrP and MO mole-
cules (Wang et al., 2012).
Rajakumar et al. reported the effective removal of heavy metal ions,
such as Pb(II), Ni(II), and Cd(II) ions using Mn2O3 doped PANI nano-
composite. The maximum adsorption capacity of PANI/Mn2O3 nano-
composite for Pb(II) (437 mg/g), Ni(II) (494 mg/g), and Cd(II)
(480 mg/g) was found to be in the optimum conditions of pH 6, tem-
perature 35 °C, adsorbent dose 60 mg, and contact time 60 min
(Rajakumar et al., 2013)
Khalili et al. evaluated the capability of PANI/Sb2O3 nanocompo-
site prepared by chemical oxidative polymerization in the presence of
hydroxypropylcellulose (HPC) for Pb(ІІ) ion removal from aqueous
media. The removal percentage of Pb(II) (92%) on the PANI/Sb2O3
nanocomposite was determined in the optimum conditions of pH 3,
temperature 25 °C, and contact time 30 min (Khalili and Eisazadeh,
2013).
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Environmental Research 162 (2018) 173–195
Gopal et al. employed the PANI coated activated carbon (PANI/AC)
nanocomposite for the removal of DR23 from aqueous solutions. The
adsorption capacity of 109.89 mg/g for DR23 was found at pH 3. The
intra particle model also proved that pore diffusion played a major role
in the adsorption of DR23 on the PANI/AC nanocomposite (Gopal et al.,
2014).
Zhu et al. presented the organic-inorganic hybrid material of PANI/
Mg/Al layered double hydroxides (PANI/LDHs) nanocomposite fabri-
cated through in-situ oxidative polymerization for the removal of Cr(VI)
from aqueous solutions. It was demonstrated that the PANI/LDHs na-
nocomposite had outstanding removal capacity toward Cr(VI)
(393.70 mg/g), comparable to Cr(VI) removal on PANI nanotubes
(198.67 mg/g) and many other materials at pH ranges between 2.5 and
5.4, adsorbent dosage 0.5 g/L and temperature 15 °C (Zhu et al., 2016).
Agarwal et al. developed the PANI/ZrO2 nanocomposite synthesized
through the chemical method, using the ammonium persulfate as an
oxidant, as an effective adsorbent for the rapid removal of MB dye. The
effects of different conditions, such as initial dye concentration, tem-
perature, and contact time were investigated. The adsorption capacity
of PANI/ZrO2 nanocomposite for MB in term of monolayer adsorption
was 77.51 mg/g at the initial concentration 30 ppm, adsorbent dosage
0.01 g, contact time 40 min and temperature 27 °C (Agarwal et al.,
2016).
Furthermore, the photo-induced adsorptive performance of PANI
based nanocomposites has been recently studied. For instance, Ghaly
et al. introduced the Ag/AgCl–PANI photoactive nanocomposite for
degradation of organic contaminants under solar light. They success-
fully synthesized the nanocomposite by deposition–precipitation reac-
tion followed by a photo-reduction method. Then, the Ag/AgCl–PANI
nanocomposite was used to degrade the MB under simulated solar light.
The effects of different parameters, such as PANI content, initial pH,
concentration of the MB solution, and catalyst dosage on the photo-
degradation efficiency were assessed. They reported that the Ag/
AgCl–PANI plasmonic photocatalyst displayed much higher photo-
catalytic efficiency than the pure PANI or Ag/AgCl. Also, a possible
mechanism was suggested for the photo-degradation of the MB under
simulated solar irradiation. The conduction band (CB) and valence
band (VB) potentials of AgCl are −0.09 and +3.16 eV (vs. NHE), re-
spectively. Also, the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) energies of PANI are
+0.8 eV and −1.9 eV (vs. NHE), respectively. Therefore, the energy
band of both AgCl and PANI matches well, which facilitates the transfer
of photo-generated electrons in the LUMO of PANI to the CB of the
AgCl. At the same time, holes on the VB of AgCl migrate to the HOMO
of PANI (Ghaly et al., 2017).
Dhanavel et al. synthesized the PANI/modified MoO3 nanocompo-
site, by a chemical oxidative polymerization method, for the photo-
catalytic degradation of MB. They expressed that PANI can absorb
visible light delivering the excited-state electrons of HOMO to LUMO.
Then, the excited-state electrons in the LUMO of PANI molecules can
drift into the CB of MoO3 and subsequently migrate to the surface of
MoO3 and react with water to produce superoxide radical, which can
oxidize the organic molecules. Here, the PANI acts as a photosensitizer,
which contributes to the higher photocatalytic activity. In fact, the
hydroxyl radicals and superoxide anions were produced by the nano-
composite catalyst leading to the decomposition of organic dyes. The
results demonstrated that 95.4% of the dye was removed after 150 min
(Dhanavel et al., 2017).
Feng et al., fabricated the reduced graphene oxide-ZnFe2O4-PANI
nanocomposites by the in-situ polymerization of Ani on the reduced
graphene oxide-ZnFe2O4 (RG/ZF) surface for the RB removal from
sewage by photocatalysis. The nanocomposite had the excellent pho-
tocatalytic activity and stability under pH = 1. After the investigation
of the photocatalytic degradation mechanisms they showed that the OH
could play an important role in the photocatalytic activity (Feng et al.,
2016).
E.N. Zare et al. Environmental Research 162 (2018) 173–195

Fig. 13. SEM images of PANI/RGO (A), PANI/α-ZrP (B) and PANI/LDHs (C) nanocomposites (Li et al., 2013b; Wang et al., 2012; Zhu et al., 2016).

Chen et al. successfully synthesized the N–K2Ti4O9/MnFe2O4/PANI
nanocomposites by an in situ oxidative polymerization method. The
photocatalytic activity was investigated by the degradation of RB under
visible light irradiation. The results showed that the binary PANI-based
nanocomposites exhibit higher photocatalytic activity as compared
with the parent materials. The separation of electron–hole pairs can be
more enhanced by mixing PANI with MnFe2O4 and N–K2Ti4O9 to form
heterojunction interfaces of N–K2Ti4O9 /PANI and MnFe2O4/PANI, and
therefore, the ternary nanocomposites displayed better photocatalytic
activity than the binary nanocomposites (Chen at al, 2014).
Zhang et al. fabricated the Ag3PO4−PANI−GO nanocomposites
with a high visible-light photocatalytic performance by a simple co-
precipitation method. The nanocomposite material exhibited better
photocatalytic properties toward both RB cationic dye and MO anionic
dye under visible light irradiation than the Ag3PO4−GO photocatalyst
did. The significant enhancement in the photoactivity can be attributed
to the differences of valence band position between Ag3PO4 and PANI
that caused a high separation efficiency of photogenerated electron–-
hole pairs (Zhang et al., 2014).
Fig. 13 illustrates the SEM images of PANI/RGO (A), PANI/α-ZrP
(B) and PANI/LDHs (C) nanocomposites showing irregular structures
(Li et al., 2013b; Wang et al., 2012; Zhu et al., 2016).
Table 13 reports the data on the sorption of heavy metal ions/dyes
by PANI/other inorganic nanoparticles nanocomposites. Accordingly,
the maximum adsorption capacity (1000 mg/g for Hg(II)) was related
to the PANI/RGO.
2.3. Proposed mechanism of pollutants adsorption by the PANI/PANI
derivatives based nanocomposites
According to the experimental results and information in literature,
we propose a possible mechanism for the adsorption of pollutants by
the PANI/PANI derivatives based nanocomposites. The chemical
structures of the adsorbents play an important role in the adsorption
phenomenon. The adsorbents containing chelating groups, such as
amine, amide, oxime, hydroxyl, thiol, carboxyl and etc. are good can-
didates for the removal of pollutants. For instance, the PANI/PANI
derivatives based nanocomposites consist of some functional groups,
such as amine, methoxy, carboxyl, hydroxyl in the main chain struc-
tures, and a physical adsorption can be assigned to them. As Fig. 14
shows, the active sites of PANI/PANI derivatives based nanocomposites
for chelating ions are amines and R groups, and therefore, the ad-
sorption can be classified as a physical adsorption.
3. Conclusions
In this review, we present a comprehensive collection of in-
expensive highly effective nanoadsorbents based on conducting poly-
mers. Among different conducting polymers, PANI and its derivatives
have been widely used for the preparation of effective nanoadsorbents
for the removal of heavy metal ions/dyes from wastewater/aqueous
solutions. Adsorption is considered one of the most effective techniques
for water treatment due to the flexibility and simplicity of design, low

Table 13
The data on the sorption of heavy metal ions/dyes by PANI/other inorganic nanoparticles nanocomposites.

Adsorbent Pollutant pH T (°C) Q (mg/g) Removal (%) Reference

PANI/MWCNTs Cr(VI) 2 40 55.5 N.R (R. Kumar et al., 2013; K.Y. Kumar et al., 2013)
PANI/RGO Hg(II) 4 25 1000 94 (Li et al., 2013b)
PANI/α-ZrP MO 4 25 377.46 N.R (Wang et al., 2012)
PANI/Mn2O3 Pb(II) 6 35 437 96.12 (Rajakumar et al., 2013)
Ni(II) 6 35 494 91.31
Cd(II) 6 35 480 89.57
PANI/Sb2O3 Pb(ІІ) 3 25 21.05 92 (Khalili and Eisazadeh, 2013)
PANI/AC DR23 3 30–45 109.89 87.27 (Gopal et al., 2014)
PANI/LDHs Cr(VI) 3 15 198.67 N.R (Zhu et al., 2016)
PANI/ZrO2 MB N.R 27 77.51 N.R (Agarwal et al., 2016)
Ag/AgCl–PANI MB 7.2 23–27 N.R 96
PANI/MoO3 MB N.R 25 N.R 90
GO-ZnFe2O4-PANI RB 1 25 8–17 90
N–K2Ti4O9/MnFe2O4/PANI RB N.R 25 18 N.R
Ag3PO4−PANI−GO RB N.R 25 N.R 98

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cost, ease of operation and insensitivity to toxic pollutants. It has been
shown that the mechanism of adsorption of heavy metal ions/dyes on
various adsorbents depends on the chemical nature of the nanoadsor-
bents and different factors including solution pH, initial concentration,
contact time, adsorbent dosage and temperature of the system. The
effects of these factors on the adsorption of heavy metal ions/dyes can
be studied by considering the optimum experimental conditions. A wide
range of nanoadsorbents based on PANI and its derivatives have been
considered for their ability to remove heavy metal ions/dyes such as Cu
(II), Co(II), Cd(II), Pb(II), As(V), Hg(II), MB, MG, MO, CR, RB, humic
acid, etc. from wastewater/aqueous solutions. Generally, the na-
noadsorbents based on PANI and its derivatives show better efficiency
for the removal of heavy metal ions/dyes. The data reported in this
review might be valuable for the design and construction of an eco-
nomical nanoadsorbent for the removal of heavy metal ions/dyes from
wastewater/aqueous solutions.
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