Applied Clay Science 198 (2020) 105838

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Applied Clay Science

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

Review article

Biopolymer-clay nanocomposites as novel and ecofriendly adsorbents for T

environmental remediation
María del Mar Ortaa, Julia Martínb, , Juan Luis Santosb, Irene Apariciob,
⁎

Santiago Medina-Carrascoc, Esteban Alonsob

a
Departamento de Química Analítica, Facultad de Farmacia, Universidad de Sevilla, C/ Profesor García González 2, 41012 Sevilla, Spain
b
Departamento de Química Analítica, Escuela Politécnica Superior, Universidad de Sevilla, C/ Virgen de África 7, E-41011 Sevilla, Spain
c
Laboratorio de Rayos-X (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes 4B, 41012 Sevilla, Spain

ARTICLE INFO ABSTRACT

Keywords: Water pollution is usually a result of human activities and it has become an issue of concern because of the toxic
Biopolymers and carcinogenic effects associated with some pollutants which may affect all living organisms. Among all the
Clays water treatment technologies adsorption is considered the most effective technique due to its affordability,
Bionanocomposites universal availability and ease of operation. Recent advances in nanotechnology have allowed the development
Adsorption
of bionanocomposites based on clay minerals and biopolymers which have emerged as promising materials for
Hazardous pollutants
Remediation
the removal of pollutants from contaminated water. Their improved properties regarding the biocompatibility
and biodegradability of biopolymers, the high surface area, increased number of active sites, and the excellent
sorption capacity of clays make the use of bionanocomposites very attractive. This review focuses on the use of
biopolymer-clays nanocomposites for environmental remediation. First, the physicochemical and structural
properties of clays and biopolymers as well as the main characterization and preparation techniques are dis-
cussed. Subsequently, the main applications of bionanocomposites as adsorbent materials for the removal of
emerging organic and inorganic pollutants from water samples are described.

1. Introduction potential adsorption materials due to their excellent properties such as

The introduction of toxic substances of synthetic or natural origin
(pesticides, hydrocarbons, heavy metals, dyes, detergents, and others)
into the environment is an alarming sign of the degradation of the
quality of the environment. The removal of these toxic chemicals from
wastewater before the discharge into aquatic ecosystems has become
imperative and, in this respect, the development of efficient technolo-
gies for the remediation of water contamination has become a main
field of study in environmental research. Major technologies, with
varying degrees of efficiency, include advanced oxidation, ion ex-
change, membrane filtration, ozonation or adsorption (Tarpani and
Azapagic, 2018). Adsorption is considered the most effective technique
for the treatment of contaminated water because of the ease of opera-
tion, low investment costs and the improved accessibility to different
adsorbents (Sophia and Lima, 2018; Tran et al., 2015). Much research is
being done on the exploration of new low-cost, more stable, safer,
ecofriendly and efficient adsorbents that can be used for pollutant re-
moval from water in batch mode processes (Sophia and Lima, 2018;
Bhat et al., 2018). Among these adsorbents, clays are considered
high surface area and cation exchange capacity (CEC), swelling, mi-
croporosity, layered structure, nano-size, as well as their lower cost
compared to conventional adsorbents like activated carbon. Ad-
ditionally, clays are suitable for large-scale applications due to their
excellent stability and safety (Awad et al., 2019).
However, natural inorganic clays are not effective for the removal of
hydrophobic organic micropollutants from water due to the hydrophilic
nature of clay surfaces. However, the nature of the interlayer space can
be modified from hydrophilic to hydrophobic by the intercalation of
alkyl long chains or functional groups to the interlayer space, which
provides clays with a wide array of new and interesting adsorbent
properties (Buruga et al., 2019; Kotal and Bhowmick, 2015). The bio-
compatibility of clays and biodegradability properties of biopolymers
makes their combination a successful approach for the development of
bionanocomposites that can be used for environmental remediation
(Ruiz-Hitzky et al., 2008a, 2008b; Darder et al., 2007; Ruiz-Hitzky and
Van Meerbeek, 2006; Ruiz-Hitzky, 2004). Among the biopolymers,
polysaccharides and polipeptides are considered the best candidates
because of their inexpensive and non-toxic properties. Since the first

⁎
Corresponding author.
E-mail address: jbueno@us.es (J. Martín).

https://doi.org/10.1016/j.clay.2020.105838
Received 4 March 2020; Received in revised form 10 August 2020; Accepted 6 September 2020
Available online 14 September 2020
0169-1317/ © 2020 Elsevier B.V. All rights reserved.
M.d.M. Orta, et al.
Fig. 1. Structure of 2:1 phyllosilicates (modified from Awad et al., 2019).
investigations on gelatin-montmorillonite (Talibudeen, 1950), collagen-
sepiolite (Herrera et al., 1995), or starch-montmorillonite (Besun et al.,
1997) hybrid nanocomposites, the research in this field of study has
advanced rapidly. A wide variety of bionanocomposites based on the
intercalation of high molecular mass biopolymers such as chitosan
(CTS), cellulose (CELL), starch (ST), alginate (ALG), sacran, zein, ge-
latin (Gel) or polylactic acid (PLA) into clay minerals such as smectites,
sepiolite, palygorskite, micas, kaolinites, and synthetic layered double
hydroxides (LDH) have been developed over the last 20 years
(Alcântara et al., 2016a; Alcântara et al., 2014a; Avérous, 2013;
Avérous and Pollet, 2012; Alcântara et al., 2012; Ray, 2012; Chivrac
et al., 2009; Chivrac et al., 2008; Darder et al., 2007; Darder et al.,
2006; Mayer, 2006; Ruiz-Hitzky et al., 2005; Siqueira et al., 2010;
Dujardin and Mann, 2002).
The control of biopolymer-clay interactions will help in the devel-
opment of smart nanomaterials for environmental applications. To date
this new type of biohybrid materials has been used for the removal of
heavy metals, reactive dyes, pesticides and even emerging pollutants
such as bisphenol A (BPA) in aqueous media (Mukhopadhyay et al.,
2020; Buruga et al., 2019; Alcântara and Darder, 2018; Shabtai and
Mishael, 2018). Additionally, some of the individual limitations of clays
and polymers (low specificity, sensitivity to pH and particle size as well
as low wettability) are improved when both materials are assembled
together to form bionanocomposites. This review describes the physi-
cochemical and structural properties of clay-biopolymer bionano-
composites and it highlights the advances for their preparation, the
methods of modification and characterization techniques as well as the
main applications in the field of environmental remediation.
2
Applied Clay Science 198 (2020) 105838
2. Clay minerals
The structure of most clay minerals is composed of well-defined
layers of linked silicate tetrahedra and octahedra shaping the clay as-
semblages. Tetrahedral layers consist of oriented, linked silica–oxygen
tetrahedra sharing three oxygens with neighboring tetrahedra and the
fourth apical oxygen is shared with an adjacent octahedral sheet via a
covalent bond. The octahedral layers are composed of aluminum, ferric
or magnesium ions in central position surrounded by a closely packed
arrangement of six oxygen atoms or hydroxyl groups. Aluminum ions
only hold two-thirds of central positions of the octahedral sheets and
the remaining one-third centers remain empty (Murray, 1991; Charles
and Lin, 1937). This property makes the octahedral layers prone to
isomorphic substitutions by metals like magnesium, which can fill all
the metal center positions in the sheet. These layers arrange themselves
into stacks with a regular van der Waals gap between them called the
interlayer or the gallery spacing. The isomorphic substitutions in the
octahedral sheets produce negative charges that are counterbalanced by
alkali or alkaline earth cations in the interlayer (Lee and Tiwari, 2012;
Ruiz-Hitzky et al., 2004).
It is the arrangement of the sheets and/or layers that differentiates
the clays, providing them with their defining characteristics and
properties. Based on their mineralogical composition, there are ap-
proximately 30 types of nanoclays with different properties that allow
different applications. The main subdivisions of the layered silicates are
done according to the type of combinations of the octahedral and tet-
rahedral sheets and the way they stack upon each other, whether the
octahedral sheet contains two or three cations per half unit cell, and
lastly to the number of isomorphous replacements and the cations in-
volved (Charles and Lin, 1937). There are seven groups of natural clay
M.d.M. Orta, et al.
minerals: (i) kaolinites, where one octahedral sheet is linked with one
tetrahedra (1:1 ratio) (e.g., kaolinite, halloysite, serpentine); (ii) non-
expanding clays, where one octahedral sheet intercalates between two
tetrahedral sheets (2:1 ratio) (e.g., mica and illite); (iii) limited ex-
panding clays (2:1 ratio) (e.g., vermiculite); (iv) strongly expanding
clays (2:1 ratio) (e.g., montmorillonite [Mt)]); (v) uncharged group (2:1
ratio) (e.g., pyrophyllite and talc); (vi) 2:1:1 group with a brucite oc-
tahedral layer between a 2:1 mineral (e.g., chlorites); and (vii) fibrous
silicates (e.g., palygorskite and sepiolite) (Mukhopadhyay et al., 2020).
The binding forces that hold the sheets forming an ‘interlayer’ are weak
van der Waals bonds. The pH and isomorphous substitutions in the
tetrahedral and octahedral sheets generate negative and positive sur-
face charges. The clay minerals included in the classification provided
above are defined as nanoscale materials having at least one dimension
at the nanometric scale (Ruiz-Hitzky et al., 2004; Murray, 1991).
Strongly expanding (2:1 ratio) clays such as Mt., hectorite or ben-
tonite, are the most commonly used layered silicates. As the forces that
hold the stacks together are relatively weak, the intercalation of small
molecules between the layers is easy. The structure of 2:1 phyllosili-
cates is shown in Fig. 1. The adsorption capacity of these natural clays
has been extensively assessed for the removal of heavy metals and polar
organic pollutants from aqueous solutions (Park et al., 2011). One of
the advantages that make clays superior to other conventional ad-
sorbents like activated carbon is their low cost and environmental
disposal of their byproducts as compared to other biological and che-
mical processes.
However, as stated in the Introduction, the hydrophilic nature of the
surface of naturally occurring clays makes them ineffective for the
adsorption of anionic, hydrophobic or non-polar organic pollutants
(Park et al., 2011). For instance, the removal efficiency of phenolic
compounds with clays is lower than the efficiency of state-of-the-art
technologies; however, it has been reported that adsorption of 2,4 di-
chlorophenol and bisphenol with clays is 10% and 40% higher than
with activated carbon and graphene/zeolites, respectively (Awad et al.,
2019).
In natural clays adsorption, is surface-related and the surface
characteristics can be modified by organic cation exchange reactions
which give rise to organoclays (Lee and Tiwari, 2012; Ruiz-Hitzky et al.,
2004; Vaia et al., 1994; Theng, 1974; Murray, 1924a, 1924b). The
negatively charged aluminosilicate layer of clays is compensated by
inorganic exchange cations (e.g. Na+ and Ca+2), which are strongly
hydrated in the presence of water. The properties of clay minerals can
Fig. 2. Classification of clay materials.
3
Applied Clay Science 198 (2020) 105838
be improved by ion exchange with cationic surfactant molecules
(usually [(CH3)3NR]+ or [(CH3)2NR2]+ where R is a hydrocarbon
substituent) intercalated between the interlayer space which results in
the surface shifting from highly hydrophilic to increasingly hydro-
phobic (Ogawa and Kuroda, 1997). In addition, in swelling clays the
intercalation of a cationic surfactant leads to increased basal spacing
and exposure of new sorption sites (Park et al., 2011). In recent years,
the adsorption capacity of swelling organomodified clays with primary
alkylamine and quaternary ammonium cations for organic pollutants
removal has been extensively studied (Park et al., 2011; Jlassi et al.,
2017; Awad et al., 2019, Martín et al., 2019a). Recently, Jlassi et al.
(2017) presented a review about preparation, modification and ad-
sorption properties of organoclays. Awad et al. (2019) reviewed the
information available about the technical viability of raw and modified
clay sorption processes. They explored the adsorption of phenolic
compounds, aromatic compounds, pesticides and herbicides, and other
organic contaminants and concluded that adsorption of clays is largely
affected by the clay properties, the kind of cationic surfactant mole-
cules, size and shape of the target pollutants, as well as the adsorption
conditions (pH, adsorbent dosage, surfactant loading, organic con-
centration, and others). The role-played for all these variables need to
be considered when assessing the sorption capacity of clays for the
removal of specific contaminants.
3. Biopolymer-clay nanocomposites
New materials with enhanced structural and functional properties
have appeared as the result of the development of innovative synthesis
strategies. A bionanocomposite is a type of hybrid material composed
by a mixture of a natural polymer or biopolymer and an inorganic solid
with at least one dimension at the nanometric scale (Ruiz-Hitzky et al.,
2008a, 2008b). These materials have been successfully incorporated
into different fields such as advanced biomedical materials (tissue en-
gineering, artificial bones or gene therapy), in controlled drug and
pesticides delivery, food processing, water purification, oxygen barrier
films or food package (Alcântara and Darder, 2018; Ucankus et al.,
2018; Ahmed and Varshney, 2010; Rhim, 2007; Ruiz-Hitzky et al.,
2005; Siqueira et al., 2010).
Among inorganic solids, special attention is given to layered mate-
rials with capacity to intercalate biopolymers and form hybrids with
functional properties (Alcântara and Darder, 2018; Darder et al., 2007;
Ruiz-Hitzky et al., 2005). Nanoclays are the main inorganic components
M.d.M. Orta, et al.
Fig. 3. Chemical structures of the biopolymers most commonly used in biocomposite preparation.
used owing to their affordability, availability, high CEC, adsorption
capacity and high surface area. The intercalation of polymers in the
interlayer space greatly enhances the adsorption characteristics of
polymer nanocomposites. Note that some of the clays shown in Fig. 2
have not been studied, since not all of the clays are useful for polymeric
composite preparation. The 2:1-type layer silicates (Mt, sepiolite, ver-
miculite or mica) and MgeAl LDH have been the types of clays more
extensively studied (Mukhopadhyay et al., 2020). As for biopolymers,
the most commonly used for bionanocomposite preparation are related
to polysaccharides such as CTS, CELL, ST and ALG (Abbasian et al.,
2017; Zafar et al., 2016; Avérous and Pollet, 2014; Chivrac et al., 2009;
Siqueira et al., 2010) proteins such as Zein or Gel (Alcântara et al.,
2016a; Alcântara et al., 2012; Darder et al., 2006; Ruiz et al., 2006) and
PLA (Avérous, 2013; Ray, 2012).. The structure of the main biopoly-
mers used is shown in Fig. 3. From an environmental standpoint,
polysaccharides are the preferred biopolymers because of their inherent
biodegradability, production from renewable sources, availability, ab-
sence of toxicity, and relatively low cost (Azhar et al., 2014; Arora
et al., 2018). Table 1 shows a summary of the characterization of the
main biopolymers and clays used as adsorbent materials.
3.1. Polysaccharides-based bionanocomposites
3.1.1. Chitosan-based bionanocomposites
CTS [poly-b(1,4)-2-amino-2-deoxy-D-glucose], the deacetylated
product of chitin, is a cationic biopolymer and the second most abun-
dant polysaccharide in nature after cellulose. Chemical modifications of
4
Applied Clay Science 198 (2020) 105838
the hydroxyl and amino groups present in CTS can improve its physical
and chemical properties. Some CTS properties include hydrophilicity,
biocompatibility, biodegradability, chelating ability, antimicrobial ac-
tivity and film forming capacity, making this polysaccharide especially
suited for application in the food and cosmetics industry, water treat-
ment, and in the biomedical field for tissue engineering and drug de-
livery (Sethy and Sahoo, 2019).
CTS is characterized by its acetylation degree and by its molecular
weight, which afecct its viscosity and solubility. In acid conditions,
when the amino groups are protonated, CTS becomes a water soluble
polycation. This property has been extensively used to elaborate CTS-
Mt hybrid materials (Chivrac et al., 2009). The binding forces between
the protonated amino groups of the CTS solution and the negative
charge on the silicate layers are mainly electrostatic interactions, but
hydrogen bonds may also play a role (Alcântara and Darder, 2018).
A great number of CTS-clay bionanocomposites have been elabo-
rated, studied and reported in the literature (Alba et al., 2019; Chen
et al., 2018; Padilla-Ortega et al., 2016; Liu et al., 2015; Deng et al.,
2012; Darder et al., 2005a; Wang et al., 2005; Darder et al., 2003).
Experiments carried out by the Ruiz-Hitzky group (Darder et al., 2005a;
Darder et al., 2003) revealed the possibility to control the intercalation
of the biopolymer as a mono- or a bilayer. They intercalated both,
monolayer and bilayer of CTS (with varying amounts) between the
individual silicate layers of Mt. and found that intercalation resulted in
an increases in the basal spacing (d001) from 1.20 nm to 1.45 nm or
2.04 nm, which corresponds the thickness of one or two polysaccharide
chains. The first CTS layer is adsorbed through a cationic exchange
 Table 1
Main biopolymers and clays used in the synthesis of bionanocomposites.
Clay/Organoclay Polymer % w:w (Clay/ Preparation method Characterization Reference
biopolymer)
M.d.M. Orta, et al.

Montmorillonite Chitosan 96:4 Solution blending method XRD; FTIR; TGA; Zeta potential Zhu et al., 2017
Chitosan/Ag 1:1 Solution blending method FTIR; XRD; SEM Azzam et al., 2016
Chitosan 1:1 Solution blending method XRD; FTIR; SEM Zhu et al., 2015
Chitosan 1:1 Solution blending method XRD; FTIR; TEM; TGA Azhar et al., 2014
Chitosan 1.23:1 Solution blending method XRD; FTIR; TEM Celis et al., 2012
Chitosan – Solution blending method XRD; FTIR; TEM; SEM Pandey and Mishra, 2011
Chitosan – Solution blending method XRD; FTIR; Zeta potencial Bleiman and Mishael, 2010
Chitosan 1:1,33 Solution blending method XRD; FTIR; TEM; SEM; TGA; AFM Yao et al., 2010
Chitosan 1:1.6 Solution blending method XRD; FTIR Monvisade and Siriphannon,
2009
Chitosan/Poly 1:7.2 In situ intercalated polymerization XRD; IR Wang et al., 2008
acrylic acid
Alginate 4:1 Solution blending method XRD; FTIR;SEM; TGA; BET Etcheverry et al., 2017
Alginate 1:1 Solution blending method XRD; FTIR; TEM; TGA Azhar et al., 2014
Alginate 4:1 Ionic gelation method FTIR Barreca et al., 2014
Alginate 3:7 Solution blending method XRD; FTIR; SEM; BET Shawky, 2011
Alginate-Aniline 1:1 Chemical oxidative polymerization XRD; FTIR; TEM; TGA Azhar et al., 2014
Starch 1:1 Solution blending method XRD; FTIR; TEM; TGA Azhar et al., 2014
Starch-Aniline 1:1 Chemical oxidative polymerization XRD; FTIR; TEM; TGA Azhar et al., 2014
Guar Gum 1:1 Solution blending method XRD; FTIR; TEM; SEM/EDX; TGA; DTG Ahmad and Mirza, 2018a
β-cyclodextrin – Solution blending method XRD; SEM; TGA;BET Shabtai and Mishael, 2018
Cellulose 2:1 Solution blending method FTIR; EDX; XRD; BET Kumar et al., 2012
Gelatin 1:1 Solution blending method XRD; FTIR; TEM; TGA Azhar et al., 2014
Gelatin-Aniline 1:1 Chemical oxidative polymerization XRD; FTIR; TEM; TGA Azhar et al., 2014

5
Kappa-carrageenan/ poly(vinyl alcohol) – – XRD; FTIR; TEM; SEM Hosseinzadeh et al., 2015
Polylactic acid – Melt-blending method WAXD; SAXS; TEM; DSC Neppalli et al., 2014
Polylactic-co-glycolic acid 3:1 Solution blending method XRD; TGA; DSC Seema, 2013
Xylan 1,25:1 Solution blending method XRD; FTIR; RC Ünlü et al., 2012
Phosphatidydylcholine – Solution blending method XRD; FTIR; TGA; NMR Wicklein et al., 2010
Bentonite Chitosan 1:1 Solution blending method FTIR; SEM; XRD; TGA Liu et al., 2015
Chitosan 20:1 Solution blending method TGA; BET Futalan et al., 2011
Chitosan 1:1 Solution blending method FTIR; SEM; BET; BJH Ngah et al., 2010a
Chitosan 1.5:1 Solution blending method XRD; FTIR; SEM Ngah et al., 2010b
Starch 1:1 Solution blending method XRD; Zeta potencial Koriche et al., 2014
Guar gum 1:1 Solution blending method XRD; FT-IR; TEM; SEM; EDX; TGA; BET Ahmad and Mirza, 2018b
Na-mica-n Chitosan 1:5 Solution blending method XRD; FTIR; TGA; MAS-NMR; Zeta- Alba et al., 2019
potential
Mica Alginate/Au 2:1 Solution blending method XRD; FTIR; TEM; SEM/EDX; TGA Ahmad and Mirza, 2017
Cellulose; Fructose 1:0,15 Solution blending method XRD; FTIR; TGA; DTA Sharma and Komarneni, 2009
Vermiculite Chitosan – Solution blending method FTIR; SEM; BET; TG-DTG; Zeta Chen et al., 2018
potential; XPS
Chitosan 35:65 Solution blending method involving XRD; ATR-IR; TEM; FE-SEM Padilla-Ortega et al., 2016
ultrasound irradiation
Chitosan 1:1 Solution blending method ATR-IR; FTIR; SEM Alcântara et al., 2014a
Hexadecyltrimethylammonium- Vermiculite Chitosan 35:65 Solution blending method involving XRD;ATR-IR; TEM; FE-SEM Padilla-Ortega et al., 2016
ultrasound irradiation
Sepiolite Sacram 1:2.7 Solution blending method ATR-IR; FTIR; SEM Alcântara et al., 2014a
Kappa-carrageenan/poly(acrylamide) – In situ-polymerization FTIR; SEM; TEM; TGA Mahdavinia and Asgari, 2013
Phosphatidydylcholine – Solution blending method XRD; FTIR; TGA; NMR Wicklein et al., 2010
Palygorskite Starch 1:1 Solution blending method ATR-IR; FTIR; SEM Alcântara et al., 2014a
Alginate 1:1 Solution blending method ATR-IR; FTIR; SEM Alcântara et al., 2014a
(continued on next page)
Applied Clay Science 198 (2020) 105838
M.d.M. Orta, et al. Applied Clay Science 198 (2020) 105838

izations; RSS: Raman spectroscopy studies; SEM: Scanning electron microscopy; TEM: Transmission electron microscopy; TGA: Thermogravimetric analysis; XRD: X-ray diffraction; XPS: X-ray Photoelectron Spectroscopy.
AFM: Atomic force microscope; ATR-IR: Attenuated total reflection-Infrared; BET: Brunauer–Emmett–Teller method; BJH: Barrett, Joyner, and Halenda method; DSC: Differential scanning calorimetry; EDX: Energy-
dispersive X-ray spectroscopy; FE-SEM: Field Emission Scanning Electron Microscopes; FTIR: Fourier transform infrared; MAS-NMR: Solid State Nuclear Magnetic Resonance spectroscopy; RC: Rheological character-
procedure, while the second layer is adsorbed in the acetate salt form
(Darder et al., 2003). Additional intercalation of more CTS layers re-
Dinari and Dadkhah, 2020
sulted in exfoliated structures (Wang et al., 2005; Darder et al., 2003).

Auta and Hamed, 2014

Moreover, the modification in the number of CTS layers allowed the
Swain et al., 2018 shift from CEC to an anionic exchange capacity (AEC). When there is an
Deng et al., 2012

Zhu et al., 2010

exchange higher than CEC, the adsorption of CTS on Mt. improves the
Li et al., 2018

absorpion of anions because the –NH3+ groups of CTS not involved in

Reference

the interaction with the negatively clay surfaces can act as anionic
exchangers (Ruiz-Hitzky et al., 2005; Wang et al., 2005). Fourier-
transform infrared spectroscopy (FTIR) analyses have confirmed the
electrostatic interactions established between both components of the
nanocomposite. The bands related to the deformation vibration (dNH3)
XRD; FTIR; TGA; DSC; Z-potencial

of the protonated amino group in the CTS structure are shifted towards
XRD; FTIR; EDX; TEM; SEM

low frequency values. Solid-state 13C nuclear magnetic resonance

(NMR) studies confirmed the exchange of the starting acetate anions
XRD; FTIR; TEM; TGA
XRD; FTIR; SEM; TGA

after treatment of this nanocomposite in a sodium nitrate solution

Characterization

XRD; TEM; SEM

(Darder et al., 2005a).

Wang et al. (2006) introduced carboxymethyl groups into CTS to
FTIR; SEM

enhance the hydrogen-bonding reaction between the matrix and –OH

group located at the edges of Mt. The Mt. was exfoliated into a large
excess of water and then mixed with a solution of carboxymethylated
CTS, but this resulted in the formation of highly flocculated structures.
According to the authors, these flocculated structures are formed by the
hydroxylated edge–edge interaction of the silicate layers.
Padilla-Ortega et al. (2016) developed functional bionanocompo-
sites based on the intercalation of CTS in natural or organically mod-
ified vermiculite (with hexadecyltrimethylammonium (HDTMA). Ul-
method
method
method
method
method
method

trasound was used for homogenization and the resulting materials were
processed as low density macroporous foams. FTIR characterization
Preparation method

blending
blending
blending
blending
blending
blending

showed that the intercalation of CTS was performed by electrostatic

attraction between the protonated amino groups and the negative
charge in the natural vermiculite layers. In the organically modified
Solution
Solution
Solution
Solution
Solution
Solution

vermiculite, stabilization was achieved by other types of interactions

with the intercalated HDTMA. Both bionanocomposites presented a
similar hydrophilic behavior, textural properties, pore distribution and
superficial morphology, however the CTS-vermiculite showed higher
thermal stability than the organovermiculite. More recently, Alba et al.
(2019) have explored the combination of brittle swelling micas and CTS
% w:w (Clay/
biopolymer)

for the preparation of eco-friendly bionanocomposites. The results from

the XRD, FTIR, and NMR spectroscopy analyses demonstrated that
1:10

when CTS is intercalated between mica layers, part of the CTS remains
1:1

1:1
1:5
–
–

bound to the mica surface by hydrogen bonds with SieO and AleO of
the basal plane. The surface coverage is quite high and the zeta-po-
tentials changed from a negative value in Na-mica to a positive value
for CTS-mica. Some authors have also combined CTS–clay nano-
composites with a hydrophilic polymer such as polyacrylic acid to
improve superabsorbent materials (Qiu et al., 2005).

3.1.2. Cellulose-based bionanocomposites

Chitosan/Fe2O3

CELL is a polysaccharide consisting in a linear polymer chain of b(1,

Starch/Ag

4)-linked D-glucopyranose monomers, and it is one of the most in-

Chitosan

Chitosan
Chitosan
Polymer

Starch

novative biopolymers for the development of adsorbents. Some of its

most attractive properties are biodegradation, biocompatibility, ab-
sence of toxicity, affordability, and production from renewable sources.
Several studies have shown that CELL nanoparticles can be used as
fillers to improve the mechanical and barrier properties of biocompo-
sites (Siqueira et al., 2010). However, CELL processing is usually
Mg-Al layered double hydroxide

complex. CELL has a very high melting point (260–270 °C) and is in-
soluble in water or in common solvents due to its partially crystalline
structure. Additionally, CELL chains are very densely packed through
Table 1 (continued)

hydrogen bonds. To overcome such drawbacks, chemical modification

Modified Ball clay
Clay/Organoclay

of the CELL structure is necessary, but because CELL decomposition

occurs at temperatures below its melting point any melt-compounding
Attapulgite

Kaolinite

technique should be avoided. Different methods can be used to obtain

non-flocculated dispersions of CELL nanocrystals in an appropriated
organic medium (Siqueira et al., 2010). One of the easiest methods for

6
M.d.M. Orta, et al.
grafting CELL is free-radical graft copolymerization which can be used
to change the behaviors and properties of CELL, allowing us for instance
to alter its hydrophobic nature and to enhance clay exfoliation process
(Abbasian et al., 2017). Park et al. (2006) used CELL acetate butyrate-
grafted-maleic anhydride as a compatibilizer to synthesize CELL-based
nanocomposites. This compatibilizer was synthesized by radical graft
polymerization of maleic anhydride monomers onto cellulose acetate
butyrate in the presence of 2,5-dimethyl-2,5-di(tert-butylperoxy)
hexane. Yoshioka et al. (2006) obtained grafted poly(ɛ-caprolactone)
chains to facilitate the clay delamination process using a combination of
in situ polymerization and solvent intercalation. Abbasian et al. (2017)
obtained a terpolymer of CELL-graft-Polychloromethylstyrene-graft-
Polyacrylonitrile/Organomontmorillonite (OMt) by grafting chlor-
omethylstyrene onto CELL using free-radical polymerization. XRD,
Transmission Electron Microscopy (TEM), and Scanning Electron Mi-
croscopy (SEM) imaging of resulting bionanocomposite showed the
absence of the peaks at 2θ = 5° characteristic of the OMt. SEM imaging
clearly showed the dispersion of the silicate layers into the polymer
matrix owing to intercalated or partially exfoliated structures.
Yadollahi et al. (2014) intercalated carboxymethyl cellulose (CMCELL)
into MgeAl LDH and NieAl LDH by co-precipitation methods. The d-
spacing increased from 0.862 nm and 0.816 nm to 1.73 nm and 2.23 nm
for Mg-Al-LDH and Ni-Al-LDH CMCELL bionancomposites, respectively.
Lastly, they found that changes in the pH from 2 to 10 resulted in in-
creased swelling of the bionanocomposites, with a dramatic increase in
swelling when pH ≥10.
3.1.3. Starch-based bionanocomposites
ST is a polysaccharide that is the primary energy reserve in plants
where the excess glucose is stored as starch in roots, tubers, seeds, and
stems. ST is composed of two glucose polymers: amylose (around of the
granule) and amylopectin, accounting for 10%–30% and 70%–90% of
the mass of a ST granule, respectively. In amylose a series of α (1–4)-
linked D-glucose units form a long linear chain with polymerization
ranging 300–10,000. Amylopectin is composed of amylose chains cross-
linked with α (1–6) bonds (Arora et al., 2018; Avérous and Pollet, 2014;
Xie et al., 2013).
A higher number of ST-based bionanocomposites have been pro-
duced, studied and reported in the literature in comparison to CELL-
clay biocomposites (Dinari and Dadkhah, 2020; Alcântara et al., 2014a;
Avérous and Pollet, 2014; Azhar et al., 2014; Koriche et al., 2014; Xie
et al., 2013; Kampeerapappun et al., 2007; Xu et al., 2005). Xu et al.
(2005) synthesized four different ST-organoclays nanocomposites by
melt-intercalation method and found that the glass transition tem-
perature increased by 6–14 °C depending on the type of clay. The in-
tercalation of ST acetate improved the thermal stability and mechanical
properties of the nanocomposite. In order to enhance the nano-disper-
sion state, bionanocomposites based on plasticized ST with polyol have
been prepared with Mt. There is a strong influence of the polyol plas-
ticizer on the exfoliation process due to the hydrogen bonds between
glycerol and Mt. platelets (Chivrac et al., 2009). Kampeerapappun et al.
(2007) prepared cassava ST-CTS-Mt bionanocomposites to promote Mt.
platelet exfoliation, which led to few clay aggregates and improved
mechanical properties. Chivrac et al. (2008) also used this method
known as “cationic polysaccharide surfactant” to promote clay ex-
foliation, using cationic ST and OMt. After organo modification, the
nanofiller was incorporated into wheat ST plasticized with glycerol by
mechanical kneading. XRD characterization showed no diffraction
peak, suggesting an exfoliated morphology. Moreover, TEM confirmed
the nanoscaled dispersion and showed that the use of this surfactant led
to a non-aggregated structure. The authors assumed that this dispersion
state is due to the preferential interactions between the OH groups of
the different starch-based biomacromolecules. Koriche et al. (2013,
2014) also prepared bionanocomposites by previous modification of ST
with cationic groups and layered clays (Mt and bentonite). XRD analysis
showed that the presence of these cationic groups promotes the
7
Applied Clay Science 198 (2020) 105838
intercalation between the silica sheets of clays via cationic exchange.
Due to an excess of positively charge from the quaternary ammonium
groups in the cationic ST structure, these bionanocomposites showed
high adsorption capacity towards anionic pollutants. Overall, nanoclay-
reinforced ST composites exhibit improved physical and chemical
properties without decreasing their biodegradation. In this respect, De
Carvalho et al. (2001) and Park et al. (2002) showed that dispersed clay
in thermoplastic ST matrix improves the mechanical, thermal, and
barrier properties of composites.
Pinto et al. (2016) synthetized a carbonaceous bionanocomposite
based on synthetic hectorite and cassava ST by pyrolysis at 850 °C. After
pyrolysis and acid digestion of clay, the resulting material had a partial
graphitic structure with almost twice the specific surface area, and up
to 20 times more mesopore volume than the carbonaceous material
obtained without the clay. Zubair et al. (2018) prepared ST-NiFe-LDH
(1:1) and ST-NiFe-LDH (2:1) by the coprecipitation method and their
adsorption capacities were compared to NiFe-LDH. The FTIR and
thermogravimetric analysis (TGA) showed better intercalation of ST
into the NiFe-LDH interlayer and increased hydroxyl and carboxyl
functional groups on the surface of ST-NiFe-LDH composites. SEM
images showed a rough and porous microstructure in ST-NiFe-LDH
composites and confirmed the presence of small cracks on the surface of
the composites, which might be associated with the reaction between
the hydroxyl groups of ST and the functional groups of NiFe-LDH
during precipitation. More recently, Dinari and Dadkhah (2020) pre-
pared an easily recoverable Fe3O4-Ag-LDH-ST bionanocomposite via an
in situ growth method. XRD and elemental mapping analysis revealed
the presence of Fe3O4 with a cubic inverse spinel structure and Ag
nanoparticles. SEM and TEM images showed that the as-synthesized
nanoparticles were spherical in shape and the TGA showed that ST
played an effective role in stabilizing the hybrid nanoparticles.
3.1.4. Alginate-based bionanocomposites
ALG is a natural polysaccharide biosynthesized by bacteria and
brown seaweeds from Phaeophyceae species. ALG consists of linear co-
polymers of units of 1,4-β-D-mannuronic acid and 1,4-β-L-guluronic
acid. Its physical properties are dependent on the sequences of these
two acids and the polymer molecular weight. ALG has numerous ap-
plications including environmental remediation due to its properties
including its biocompatibility, low toxicity, chelating activity, and hy-
drophilicity (Ucankus et al., 2018).
Following a co-precipitation method, ALG has been successfully
trapped between the ZnAl LDH layers. This method consists of the
“coorganized assembly” synthesis of the LDH in the presence of the
polymer (Leroux et al., 2004). An interesting feature of the resulting
ALG-LDH nanocomposites is that the characteristic AEC of the pristine
LDH is reversed to a CEC (Darder et al., 2005b; Leroux et al., 2004;
Leroux and Besse, 2001) due to the strong electrostatic interactions
between the negatively charged carboxylate groups of ALG and the
positively charged sites of the LDH sheets (Darder et al., 2005b; Leroux
et al., 2004). Alcântara et al. (2014a) evaluated the effect of the in-
corporation of sepiolite and palygorskite (fibrous clays) into neutral
(ST), cationic (CTS), and negatively anionic (ALG) polysaccharide
matrices and found that interactions occur between the hydroxyl
groups in the biopolymer backbone and the silanol groups on the clay
surface. In the case of ALG and CTS the presence of other functional
groups, carboxylate and amino groups, respectively, may be also in-
volved in the interactions, as shown by FTIR spectra. The incorporation
of clays also resulted in increased viscosity, indicative of the formation
of hydrogen bonds. These interactions led to improved mechanical
properties and higher degree of water resistance of these biomaterials
compared to pure biopolymer films.
Ahmad and Mirza (2017) developed a novel and ecofriendly ALG-
Au-mica bionanocomposite with improved mechanical strength. Au
nanoparticles were incorporated due to the excellent biocompatibility,
easy preparation and adsorbent capacity owing to their large specific
M.d.M. Orta, et al.
surface area. Au nanoparticles were synthesized via green procedures
using glutathione and oxalic acid. SEM images revealed a hetero-
geneous cross-linked structure with dispersed Au nanoparticles. TGA
analysis also showed that the synthesized bionanocomposite decom-
poses at higher temperature with good thermal properties as compared
to pure ALG.
In another attempt, Darder et al. (2017) prepared a bionano-
composite based on ALG, potato ST and sepiolite as reinforcing filler by
lyophilization and that exhibited low density and mechanical and fire
resistance. FTIR analysis confirmed the strong interaction between the
clay and the polysaccharide chains through a highly perturbed
stretching vibration band of −OH in the silanol groups of sepiolite. The
authors also observed that the porosity of the biomaterial can be
modulated by varying the sepiolite content, with decreased porosity as
the sepiolite content increased thereby allowing the modulation of
certain properties like mechanical resistance.
3.1.5. Xanthan gum-based bionanocomposites
Xanthan gum (XG) is a natural polysaccharide whose backbone is a
β-(1–4)-D-glucose (CELL). Every alternate glucose residue has a side
chain of two mannoses and one glucuronic acid residues. XG is con-
sidered an anionic polyelectrolyte. Its excellent properties (availability,
affordability, biodegradability and the presence of hydrophilic func-
tional groups–OH and –COOH) make this natural gum suited for dif-
ferent applications (Ahmad and Mirza, 2018a, 2018b, 2018c).
Ahmad and Mirza (2018a) developed a novel XG-Mt bionano-
composite that appeared as a densely bounded network structure with
porous and irregular surface on SEM images and highly dispersed
particles on TEM images. The same authors also reported that grafting
with functional glutathione (with amine, thiol, and carboxylate groups)
could increase the adsorption capacity of XG (Ahmad and Mirza,
2018a). They prepared and characterized a XG-Glutathione-Zeolite
bionanocomposite which was effectively applied for the adsorption of
heavy metals. They also synthetized a XG-n-acetyl cysteine-modified
mica which increased metal chelation and the number of binding sites
(Ahmad and Mirza, 2018b). The SEM image of the bionanocomposite
revealed a highly irregular surface that became smoother after Pb(II)
loading, suggesting a successful adsorption of Pb(II).
Liu et al. (2011) prepared a macroporous foam from CTS-XG-Mt via
freeze-drying. Their results suggested that the main factor governing
the structural hardness was the freezing rate during preparation. Slow
cooling rate during freezing led to larger pore sizes and a more tilted
pore arrangement. XRD and TEM characterization was consistent with
an exfoliated structure. Mt. also improved the hardness of the prepared
foams.
3.1.6. Cyclodextrin-based bionanocomposites
β-Cyclodextrin (βCD) is an oligosaccharide formed by seven glucose
units linked by α-(1,4) glycosidic bonds in a cyclic structure. βCD has
an internal hydrophobic cavity (0.78 nm width) that allows the for-
mation of a size-specific inclusion complex between βCD and hydro-
phobic molecules. The possibility of cross-linking or anchoring βCD to
solid supports allows the formation of insoluble sorbents with higher
adsorption capacity for the removal of micropollutants than activated
carbon (Shabtai and Mishael, 2018).
Shabtai and Mishael (2018) designed a novel composite sorbent
based on Mt. and neutral (pCD0) or cationic (pCD+) CD by crosslinking
βCD with epichlorohydrin and incorporated cationic glycidyl tri-
methylammonium chloride (GTMAC) groups. The incorporation of
GTMAC significantly decreased the polymer molar mass and hydro-
dynamic radius, confirmed by 1H NMR and FTIR analysis. pCD0 showed
better adsorptive properties than pCD+ due to the electrostatic repul-
sion between the highly charged chains of pCD+ and because of the
preferential adsorption of higher molar mass pCD0 (Shabtai and
Mishael, 2018). The XRD analysis showed that the increase in basal
spacing upon adsorption of pCD+ (1.92 nm) was only slightly larger
8
Applied Clay Science 198 (2020) 105838
than the height of a βCD cavity (0.8 nm), which indicated that the
polymer is tightly intercalated between the clay layers. XRD showed no
clear diffraction and increasing intensity at low angles upon adsorption
of the pCD0, indicating exfoliation of the clay structure resulting from
polymer adsorption in a very extended conformation. pCD+-Mt was
characterized by a dense, compact structure of closely packed clay
tactoids while pCD0-Mt was characterized by an open, fluffy structure
of loosely aggregated clay tactoids. Prior to the investigations of
Shabtai et al., hybrids of sepiolite with modified CD (randomly me-
thylated) had been explored by Mura et al. (2016) for improving ox-
aprozin dissolution properties and, consequently, its therapeutic effi-
ciency and safety.
3.1.7. Carrageenan-based bionanocomposites
Carrageenans are a family of linear sulfated polysaccharides ob-
tained from a red seaweed which are also widely used in the food in-
dustry. Electrostatic interactions occur between the negatively charged
carrageenan and positively charged molecules. There are many studies
available on the interactions of carrageenans with different cationic
compounds, but there is little literature about their use as adsorbents
for the removal of organic pollutants from water.
As for ALG, bionanocomposites based on i-carrageenan-Zn–Al LDH
have also been prepared by co-precipitation methods (Darder et al.,
2005b). The incorporation of carrageenans resulted in non-intercalated
and poorly crystallized materials (Darder et al., 2005b; Ruiz-Hitzky
et al., 2005). XRD analysis showed that i-carrageenan seems to be in-
corporated as a bilayer or, most likely, as a double helix (ΔdL of 1.2 nm)
within the LDH structure.
Since kappa-carrageenan contains high contents of sulfate and hy-
droxyl functional groups, it may potentially be miscible with poly(vinyl
alcohol) (PVA) due to the formation of hydrogen bonds. PVA has been
extensively used in many biomaterial applications due to its unique
properties such as easy preparation, good biodegradability, and ex-
cellent mechanical and chemical resistance (Park et al., 2001).
Hosseinzadeh et al. (2015) developed a hybrid kappa-carrageenan-
PVA-Mt nanocomposite by crosslinking the polymers with the free-
zing–thawing technique and subsequently with K+ ions. The FTIR
analysis revealed the interactions of Mt. with the functional groups of
kappa-carrageenan and PVA and XRD and TEM images showed a
layered morphology due to the penetration of polymer chains into Mt.,
which showed an intercalated and exfoliated structure.
3.2. Protein-based bionanocomposites
3.2.1. Zein-based bionanocomposites
Zein is the primary storage protein of maize. This globular protein,
with its greater concentration of nonpolar amino acids, is 50-fold more
hydrophobic than other proteins like albumin or fibrinogen. Zein is
insoluble in water but soluble in aqueous ethanol (60–95% (v/v)),
aqueous solution at pH > 11, some organic polar solvents (e.g., pro-
pylene glycol and acetic acid) and certain anionic detergents (Shukla
and Cheryan, 2001). Its molecular weight ranges between
23,000–27,000 Da, and this protein has already been used in many
applications such as adhesives and cosmetics, and to generate drug-
delivery matrices alone or in combination with other compounds. Zein
is also used in the food industry because of its ability to form hydro-
phobic grease-proof coatings and biodegradable films that provide a
barrier to moisture and oxygen. Because of these characteristics, the use
of zein might be a promising method to reduce the hydrophilicity of
pristine clays, as in conventional organoclays with long-chain alky-
lammonium cations (Alcântara, 2013; Alcântara et al., 2012).
In 2012, Alcântara et al. combined zein with two fibrous clays
(sepiolite and palygorskite) and found that the amount of adsorbed zein
can be adjusted to ensure the complete coverage of the clay fibers, but
zein aggregates were found at high equilibrium concentration of zein.
Due to the higher external surface area of the zein-sepiolite
M.d.M. Orta, et al.
nanocomposites, they exhibit larger amount of assembled protein than
zein-palygorskite. The assembling mechanism is related to the inter-
action of the amide groups of zein with silanol groups on the surface of
the fibrous clays. In the same work the authors also studied the prop-
erties of zein–fibrous clay biohybrids as additives in the preparation of
nanocomposites when using ALG as a polymer matrix (Alcântara et al.,
2016a; Alcântara et al., 2012). The ALG-Zein-fibrous clay bionano-
composite showed reduced water vapor transmission and improved
barrier properties towards oxygen even at high humidity conditions.
The intercalation of zein on Mt. is a complex process which is in-
fluenced by the structural stability of the protein, the ionic strength, the
pH value as well as the surface properties. The same authors (Alcântara
et al., 2016b) prepared a zein-Mt biohybrid following two synthesis
methods (Alcântara et al., 2016b): 1) using zein dissolved in 80% (v/v)
ethanol/water solution, and 2) using a sequential process that involves
the previous separation of zein components in absolute etanol. The
latter resulted the most effective method. Their results also suggested
that these bionanocomposites could be associated with other polymers
of different nature, representing a promising eco-friendlyalternative to
organoclays based on alkylammonium cations.
3.2.2. Gelatin based bionanocomposites
Gelatin (Gel), a natural polymer, is the denatured form of the pro-
tein collagen and its constituents are amino acids such as glycine,
proline, hydroxyproline, glutamic acid and arginine. The growing in-
terest in Gel is due to its low antigenic capacity. However, like carra-
geenan, there is little literature about its application in the environ-
mental remediation field.
The investigations on the interactions between Gel and layered si-
licates in 1950 (Talibudeen, 1950) laid the basis for the development of
novel Gel-based bionanocomposites derived from clay minerals and
layered perovskite (Darder et al., 2006; Ruiz et al., 2006). The assembly
Gel-perovskite results in a dielectric permittivity greater than the in-
crease in the dielectric loss values in biohybrid films, which makes it
useful in the microwave industry or in high-frequency devices (Ruiz
et al., 2006).
The experiments conducted by the Ruiz-Hitzky group showed that
the uptake of Gel by clay minerals is influenced by the pH, whose values
must be adjusted below the isoelectric point of the biopolymer. For
instance, the intercalation of Gel in homoionic smectites or in Mt. oc-
curs at low pH values required to protonate the amino groups of the
protein. Thus, the positively charged biopolymer is able to replace to-
tally or partially the sodium ions mainly located on the interlayer space
of the clays (Ruiz-Hitzky et al., 2005; Weiss, 1969; Talibudeen, 1950). It
has been suggested that intercalation of proteins into Mt. may result in
distortions and other structural disturbances in the proteins due to their
confinement in the interlayer space of the clay (Theng, 1979). Ruiz-
Hitzky et al. (2005) suggests that these parameters and those related
with the expected loss of entropy associated to the intercalation process
should be investigated using advanced spectroscopic techniques such as
solid state high resolution NMR combined with microcalorimetric
measurements.
3.3. Polylactide-based bionanocomposites
PLA is formed by polymerization of monomers of lactic acid (LA)
obtained from bacterial fermentation of carbohydrates. PLA is a ther-
moplastic polyester completely biodegradable and bioabsorbable that
derives from renewable sources (Avérous, 2013, Ray, 2012; Ahmed and
Varshney, 2010). High molecular weight PLA is synthesized by ring-
opening polymerization of LA, normally using aluminum and tin alk-
oxides as catalysts. PLA was one of the first biodegradable man-made
polymers because of its renewable origin, controlled synthesis, me-
chanical properties, and inherent biocompatibility (Ray, 2012). The
intercalation of clays with PLA allows the development of bionano-
composites with enhanced properties such as improved storage
9
Applied Clay Science 198 (2020) 105838
modulus, tensile strength, break elongation, crystallization rate, and
other mechanical properties. More importantly, the presence of clay
decreases the gas and water vapor permeation, increases the heat dis-
tortion temperature and scratch resistance, and controls the biode-
gradation of the PLA matrix.
Neppalli et al. (2014) prepared different (PLA)-based nanocompo-
sites filled with different kinds of cationic (Mt) and anionic (perkalite)
clays. A similar degree of dispersion was achieved in both types of clays
but different structural and morphological changes. Perkalite induced
higher crystallinity, a faster crystallization rate and also a modification
of the crystallization mechanism with preservation of the lamellar
framework of PLA while Mt-based nanocomposites resulted in dis-
ordered lamellar stacks. Perkalite-PLA also underwent faster degrada-
tion than either the PLA matrix or the Mt-PLA. These findings show that
the choice of the chemical nature of the nanofiller allows us to mod-
ulate both the degradation rate of PLA and its structure.
Bionanocomposites based on PLA-LDH with improved mechanical
and thermal properties have also been investigated but to a lesser extent
than natural clays. The studies availabe are very limited and because of
the strong electrostatic interactions between the highly charged hy-
droxyl layers and intercalated anions the delamination of LDH layers at
the nanolevel is very difficult to achieve (Ray, 2012; Chiang and Wu,
2010; Zhou and Xanthos, 2010).
4. Methods for preparation of biopolymer-clay nanocomposites
Nanofiller dispersion is largely dependent on the physical and
chemical affinitty between the clay material and the polymer matrix
and the preparation method. Depending on the interactions between
nanofiller and polymer matrix, the following types of composite can be
described (see Fig. 4):
Phase-separated microcomposites are formed when the polymer is
unable to intercalate between the silicate sheets. As the individual
layers are not separated, the clay agglomerates act as microparticles
dispersed in the polymeric matrix. For this reason, these composites are
frequently named “microcomposites”. This lack of uniform dispersion
makes their properties particularly poor (Valapa et al., 2017).
Intercalated nanocomposites are obtained when polymer chains are
inserted between the sheets of the layered clay resulting in an enhanced
interlayer distance (Valapa et al., 2017).
Exfoliated nanocomposites are produced when individual clay layers
are separated from one another and are homogeneously dispersed
within the polymer matrix. This homogeneous dispersion provides na-
nocomposites with enhanced mechanical, thermal, and barrier prop-
erties. However, complete exfoliation is usually challenging (Valapa
et al., 2017).
To enhance the intercalation/exfoliation process into a polymer
matrix, a chemical modification of the clay surface to match the
polymer polarity, is often conducted (Alexandre and Dubois, 2000).
Cationic exchange is the most common technique, but other methods
such as organosilane grafting (Dai and Huang, 1999), the use of iono-
mers (Shen et al., 2002) or block copolymers adsorption (Fisher et al.,
1999) have also been used (Valapa et al., 2017; Chivrac et al., 2009). In
this sense, Chivrac et al. (2009) provided us with an in-depth review of
the main strategies used to develop polysaccharide-based biocompo-
sites with Mt. with a discussion of their dispersion state and properties.
There are three main methods for the clay incorporation into the
polymer matrix: (i) solution blending; (ii) polymer melt blending; and
(iii) in situ polymerization method (Bhawani et al., 2018; Guo et al.,
2018; Ojijo and Ray, 2013; Chivrac et al., 2009; Alexandre and Dubois,
2000). As shown in Table 1, solution blending is the most appropriate
for biopolymers.
4.1. Solution-blending
In this method, the polymer is dissolved in a suitable solvent,
M.d.M. Orta, et al.
Fig. 4. Schematic showing the polymer-clay nanocomposite morphologies: flocculated, intercalated and exfoliated (modified from Valapa et al., 2017).
typically water for biopolymers, and the clay is simultaneously dis-
persed in the same solvent or a different one to obtain a miscible so-
lution. The polymer solution is then intercalated between the clay
dispersion. The resulting solution is homogenized and the solvent
evaporated (Valapa et al., 2017). For non water-soluble polymers, this
process involves the use of large amount of organic solvents, which is
environmentally unfriendly and costly (Bhawani et al., 2018). More-
over, a small amount of solvent may remain in the final product at the
polymer-clay interface thus reducing the interactions between the
polymer and the clay surfaces (Jin et al., 2002).
As mentioned above, solution blending is the most common method
(see Table 1) because many of the biopolymers used to produce hybrid
bionanocomposites, such as CTS, CELL or pectin, cannot be melt pro-
cessed due to high thermal or thermo-mechanical degradations. The use
of in-situ polymerization is also limited as most biopolymers are natu-
rally availabe in the polymeric form rather than as monomers (Chivrac
et al., 2009). Fig. 5A shows a schematic of the solution-blending
method.
4.2. Melt-blending
Melt blending is a high temperature process where the clay is in-
corporated simultaneously to the annealed polymer matrix into a melt
mixing device and the resulting composite is kneaded for homogeneous
distribution (Valapa et al., 2017). Two parameters can be used for
optimization of clay dispersion (Soetaredjo et al., 2018): the residence
time and the shearing. The first one is needed to allow diffusion of the
polymer chains into the inter-layer gallery to obtain an exfoliated
10
Applied Clay Science 198 (2020) 105838
morphology. The latter helps to induce platelet delamination from the
clay tactoids. This method is eco-friendly because no solvent is in-
volved, but the thermal or thermo-mechanical inputs result in partial
degradation of chains and the high residence times required for clay
exfoliation induce matrix degradation. These drawbacks make this ap-
proach unsuitable for biopolymers, except for PLA or the thermoplastic
ST modified by additives (Dang et al., 2020; Ren et al., 2018; Neppalli
et al., 2014). Fig. 5B shows a schematic of the melt-blending method.
4.3. In-situ polymerization
In a first stage clays are swollen into a monomer solution where
polimerization starts and propagates (Chivrac et al., 2009). The poly-
merization initiating agent can be heat or a suitable chemical
(Soetaredjo et al., 2018). The molecular weight of macromolecules in-
creases, leading to a d001 increase and sometimes to an almost fully
exfoliated morphology (Ray and Okamoto, 2003). This method has
been applied as an alternative to melt blending for in situ poly-
merization of intercalated LA monomers for the formation of exfoliated
systems (Paul et al., 2005). As mentioned above, the polysaccharide
chains are naturally formed during plant growth and are extracted from
plants already in their polymeric form making this technique unsuitable
for the preparation of polysaccharide-based bionanocomposites
(Chivrac et al., 2009). Fig. 5C shows a schematic of the in-situ poly-
merization method.
Other non-traditional preparation techniques such as electrospin-
ning and processing under supercritical conditions (e.g., supercritical
carbon dioxide), microwave-induced, one-template-directed, self-
M.d.M. Orta, et al.
Fig. 5. Techniques for bionanocomposite preparation: (A) solution blending; (B) melt blending; (C) in-situ polymerization (reproduced from Valapa et al., 2017 with
permission).
assembly or intermatrix synthesis have been developed in order to
shape the material in the desired configuration (Bhawani et al., 2018).
5. Characterization techniques of biopolymer-clay
nanocomposites
A key issue in polymer-clay nanocomposite research is the de-
termination of the properties related to the adsorption behavior such as
morphology, expansion capacity, layer charge and charge arrangement,
pore size and pore arrangement. The most commonly methods applied
for characterization of clays are XRD, TEM, SEM, FTIR, NMR, and TGA
(Alexandre and Dubois, 2000)..
Due to its ease of operation and availability, XRD has been widely
employed to evaluate the resulting hybrid structure after dispersing the
nanofiller in the polymeric matrix (Bee et al., 2017). Through the
evaluation of the presence and shift of the basal reflections we can
determine the type of nanocomposite structure (phase-separated, in-
tercalated, or exfoliated). XRD can also be used to examine the kinetic
properties of the polymer melt blending. The intensity and shape of the
basal reflections are indicative of the degree of dispersion of the na-
nofiller within the polymer matrix. For example, for exfoliated struc-
tures, the disappearance of the diffraction peak suggests the complete
distribution of clay aggregates in the polymer matrix with the disrup-
tion of the layer structure of the clay. For intercalated structures, the
expansion of the interlayer spacing after polymer intercalation is de-
monstrated by the shift of the basal reflections towards lower diffrac-
tion angles. In contrast, for conventional microcomposite structures, the
basal reflections remain unchanged. This is due to the clay aggregates
retaining their stacking arrangement because the polymer chains
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Applied Clay Science 198 (2020) 105838
cannot access the interlayer space (Bee et al., 2017).
However, in some cases the XRD analysis alone is not reliable en-
ough to determine nanocomposite structure because it does not provide
information about the spatial orientation of the silicate layers, which
complicates the interpretation of data. For example, when mixed-clay
morphologies are obtained the measurement of the interlayer spacing
might be inaccurate as the basal reflections originate from different
components. Additionally, the absence of diffraction peaks in randomly
distributed intercalated clays might lead to wrongly identify structures
as exfoliated. Lastly, clay dilution can also result in peak broadening or
peak absence even without delamination (Bee et al., 2017).
XRD should be complemented with TEM because this technique can
provide qualitative information about the morphological features and
spacial arrangement of the clay as well as visual information of any
internal flaws. The main advantages of TEM are its magnifica-
tion—typically between 50,000 to 10,000,000×—and the ability to
visualize specimens and to provide diffraction data. TEM images allow
the visualization of the spatial distribution of clay layers. Clay layers
show strong contrast because they consist of elements with high atomic
number (Si, Al and O), whereas the polymer matrix basically contains
C, H and N. Consequently, the intersections of clay layers appear as
dark lines. TEM images of phase-separated composites are darker owing
to the presence of clay aggregates resulting in electron scattering. In
contrast, TEM of exfoliated composites shows brighter images owing to
the homogeneous dispersion of clay layers within the polymer matrix.
As with TEM, SEM also relies on the use of high-energy electrons to
generate images of the surface of solid specimens as well as providing
information about their dispersion, crystalline structure, composition
and orientation (Bee et al., 2017). However, due to the limited
M.d.M. Orta, et al.
resolution of SEM instruments (around 1 nm), detailed information of
the nanoparticle distribution within the polymer matrix is difficult to
obtain. In contrast, it is useful for imaging fractured surfaces. Recently,
a combination of SEM and energy dispersive X-ray spectroscopy is
being used to determine the degree of dispersion of nanoparticles on the
fractured surface of bionanocomposites (Ojijo and Ray, 2013).
FTIR spectroscopy is also used to understand the structure of the
polymer nanocomposite allowing us to differentiate between the
bonding in a polymer from the bonding in a nanocomposite. This
technique is fast and involves minimal sample preparation and as a
result has become a well-accepted method for sample characterization.
However, the bonding differentiation may be difficult to understand
even though intercalation has already occurred. As mentioned in pre-
vious sections, multiple studies have used FTIR for characterizing the
bands attributed to the intercalated biopolymer in the clays structure
(Alba et al., 2019; Wang et al., 2005; Darder et al., 2003). This tech-
nique is very helpful to determine the electrostatic interactions between
byopolimers and clays. Darder et al. (2017) used FTIR to assess the
interactions between sepiolite and ST and ALG and found a consider-
able perturbation of the stretching vibration band of the silanol groups
located at the sepiolite surface, which suggest that the interactions
occur between the external OH groups of the silicate and the hydroxyl
groups of the polysaccharide chains. The band was shifted towards
lower frequency values, leading to a decrease in absorbance with re-
spect to that assigned to the stretching vibration of Mg-OH that remains
unaltered. In another attempt, Darder et al. (2005b) and Leroux et al.
(2004) observed using FTIR measurements strong electrostatic inter-
actions between the negatively charged carboxylate groups of ALG and
pectin biopolymers and the positively charged sites of the LDH sheets,
while a weak interaction was observed between the i-carrageenan and
the LDH.
Bulk characterization techniques such as NMR are also be used to
evaluate the morphology, surface chemistry, and the quality of clay
dispersion by the measurement of the 1H, 13C, 23Na, 27Al or 29Si spin-
lattice relaxation time (T1) (Ray and Okamoto, 2003). VanderHart et al.
(2001) first used NMR (1H and 13C) to quantify the degree of clay ex-
foliation of nylon 6-Mt nanocomposites and found a potential re-
lationship between measured T1H values and the quality of the clay
dispersion. When the clay particles are stacked and poorly dispersed in
the polymer matrix, the average distances between polymer-clay in-
terfaces are greater, and the average paramagnetic contribution to T1H
is weaker (Ray and Okamoto, 2003). Alba et al. (2019) used 29Si and
23
Na magic angle spinning (MAS)-NMR spectroscopy to show CTS in-
corporation into mica but part of the biopolymer remains at the outer
surface where it binds to the SieO and AleO of the basal plane. On the
other hand, as mentioned above, both FTIR and 13C NMR determina-
tions also help to confirm the ability of CTS–smectite nanocomposite to
act as an anionic exchanger when the biopolymer is arranged as a bi-
layer in the interlayer space (Darder et al., 2005a).
Finally, TGA provides information about the thermal stability of
bionanocomposites. There are many studies that have shown the in-
creased stability of biopolymers in bionanocomposites. Intercalation of
biopolymers into clay mineral layers increases the decomposition
temperature in 40–50 °C as the clay acts as a heat barrier in the na-
nocomposite structure, which enhances the overall thermal stability of
the system, and helps in the formation of char after thermal decom-
position. Initially, this heat barrier effect increases the decomposition
temperature and subsequently it serves as a heat source to accelerate
the decomposition process, in conjunction with the heat flow supplied
by the outside heat source (Ray and Okamoto, 2003). Typical TGA
curves show degradation, measured as mass loss, as a function of
temperature (dynamic heating) or time (isothermal heating). The mass
loss that occurs between ambient temperature to around 170 °C is as-
sociated with the loss of water from the surface and interlayers, water
retained in the biopolymers and intersticial water. The process of
thermal decomposition of the system depends on the biopolymer and
12
Applied Clay Science 198 (2020) 105838
clay used in the formulation. In general, the breakdown of the biona-
nocomposite begins at approximately 250 °C with the decomposition of
organic components and finishes at approximately 600–630 °C with the
destruction of the crosslinked network structure and the complete
breakage of clay mineral chains (Li et al., 2018; Swain et al., 2018;
Darder et al., 2017; Mahdavinia et al., 2016; Azhar et al., 2014; Ray and
Okamoto, 2003). Lastly, several authors have examined the thermal
stability of ST-based nano-biocomposites to establish the relationships
between clay dispersion and thermal stability. Park et al. (2002) used
TGA to show the higher degradation temperature of potato ST-Mt and
OMt in comparison to the neat matrix. Moreover, thermal stability of
potato ST-Mt was higher than OMt which suggests a relation between
Mt. dispersion and thermal stability.
6. Applications of biopolymer-clay nanocomposite as adsorbents
Technological advances in analytical methods have made possible
to detect and quantify a wide range of chemicals in the various en-
vironmental compartments. These chemicals include pesticides, heavy
metals, polycyclic hydrocarbons, dioxins, and others as well as those
known as “emerging contaminants” (plasticizers, flame retardants,
perfluorinated compounds). An extensive number of publications have
described levels of contaminations worldwide and in all the environ-
mental compartments. Adsorption is considered one of the most effec-
tive techniques for the treatment of contaminated water, with the de-
velopment of novel adsorbents in recent years (Guo et al., 2018). In this
respect, biopolymer-clay nanocomposites have shown high adsorption
capacity and long life cycle owing to their easy regeneration, effective
cation exchange, large surface area, and relative affordability and lack
of toxicity.
The adsorption capacity, selectivity and recovery of bionano-
composites is largely affected by (1) the modification technique, the
presence of exchangeable cations, nanoclay morphology, and the pre-
sence of water molecules in the interlayer; (2) pH, temperature, ionic
strength, pollutant concentration, and the presence of other ions or
compounds. There are multiple mechanisms involved in the adsorption
process, including electrostatic attraction, Lewis acid-base interaction,
hydrogen bonds or ion-exchange. Table 2 shows a summary of scientific
papers on bionanocomposites as adsorbent materials for the removal of
emerging organic and inorganic pollutants such as pesticides, BPA,
hydrophobic organic pollutants, dyes or heavy metals, from water
samples. The adsorption of the different contaminants is discussed
below.
6.1. Pesticides
Pesticides have been extensively used to evaluate the efficacy of
bionanoacomposites as adsorbent materials. Organophosphate pesti-
cides have largely replaced organochlorine pesticides because of the
persistence and accumulation of the latter in the environment. One of
the first studies on bionanocomposite adsorption capacity was the one
by Alcântara (2013) who developed a bionanocomposite with zein-se-
piolite modified with magnetite nanoparticles. The main properties of
this magnetosorbent are its water stability and the mechanical prop-
erties owing to the reinforcement provided by sepiolite fibers. The re-
sulted material has been successfully applied to adsorb 4-chloro-2-me-
thylphenoxy-acetic acid, indicating their application in environmental
remediation (Alcântara, 2013). One of the main advantages of this type
of adsorbent is that it can be easily recovered from the aqueous media
by applying an external magnetic field.
Acidic pesticides are weakly sorbed to soil, which increases the risk
of contamination of ground and surface water. Sorption depends on pH
and acidic pesticides are usually found in their anionic form at the pH of
soil and water environments (Celis et al., 2012). Clay-based adsorbents
usually show a high affinity for cationic and very polar pesticides, but
low affinity for anionic pesticides owing to the negative charges on the
 Table 2
Adsorption experiments on biopolymer-clay composites as adsorbent materials for the removal of organic and inorganic pollutants from water.
M.d.M. Orta, et al.

Group Analyte Bionanocomposite Qmax (mg/g) Isotherme Kinetic Reference

Pesticides Paraquat Mt/ALG 74.3 Langmuir – Etcheverry et al., 2017

Clopyralid Mt/CTS 96.0 Freundlich – Celis et al., 2012
Dicamba Laponite/ST 251.9 Langmuir Pseudo- second order Pinto et al., 2016
Phenols and hydrophobic organic pollutants Bisphenol A Mt/β-CD+ 0.1 Langmuir Pseudo-second order Shabtai and Mishael, 2018
4-nitrophenol Ag/LDH/ST – – – Dinari and Dadkhah, 2020
Phenol Mt/CTS 11.0 – – Zhu et al., 2017
PCB 3-Cl Mt-ALG 332.6 Langmuir Pseudo-second order Barreca et al., 2014
PCB 4 Cl Mt-ALG 70.0 Langmuir Pseudo-second order Barreca et al., 2014
PCB 5 Cl Mt-ALG 55.0 Langmuir Pseudo-second order Barreca et al., 2014
PCB 6 Cl Mt-ALG 44.9 Langmuir Pseudo-second order Barreca et al., 2014
Dyes Crystal violet Bentonite/Guar gum 167.9 Langmuir Pseudo-second order Ahmad and Mirza, 2018a
Conger red Mt/CTS 350.0 – – Zhu et al., 2017
Crystal violet Mt/CTS 450.0 – – Zhu et al., 2017
Amido Black 10B Bentonite/CTS 323.6 Langmuir Pseudo-second order Liu et al., 2015
Reactive black 5 Mt/CTS – – – Zhu et al., 2015
Crystal violet Sepiolite-Kappa-carrageenan-g-poly(acrylamide) 47.0 Langmuir Pseudo-second order Mahdavinia and Asgari, 2013
Methylene blue Modified Ball clay/CTS 142.0 Langmuir Pseudo-second order Auta and Hamed, 2014
Basic blue 9 Mt/CTS 700.0 – – Monvisade and Siriphannon, 2009
Basic blue 66 977.0
Basic Yelow 300.0
Methylene blue Mt/CTS-g-poly 1859.0 Langmuir Pseudo-second order Wang et al., 2008
(acrylic acid)
Tartrazine Bentonite/CTS 294.1 Langmuir Pseudo-second order Wan Ngah et al., 2010a

13
Malachite green Bentonite/CTS 435.0 Langmuir Pseudo-second order Wan Ngah et al., 2010b
Methyl Orange Chitosan Kaolin/γ-Fe2O3 14.2 – – Zhu et al., 2010
Inorganic methals Cr(VI) Red palygorskite/CTS-g-PMMA 92.5 – – Sethy and Sahoo, 2019
Pb(II) Bentonite/Guar gum 18.9 Freundlich Pseudo-second order Ahmad and Mirza, 2018a
Cu(II) Mica/ALG 169.8 Langmuir Pseudo-second order Ahmad and Mirza, 2018b
Pb(II) Vermiculite/CTS 166.7 Langmuir Pseudo-second order Chen et al., 2018
Cd(II) Vermiculite/CTS 58.5 Langmuir Pseudo-second order Chen et al., 2018
Se(IV) LDH/CTS 17.0 Langmuir Pseudo-second order Liu et al., 2015
Se(VI) 12.0 Langmuir Pseudo-second order
Pb(II) Mica/ALG 25.7 Freundlich Pseudo-second order Ahmad and Mirza, 2017
Cd(II) Mt/CTS 8.0 – – Zhu et al., 2017
Cu(II) Mt/Fe3O4-ST-polyamidoxime 158.7 Langmuir Pseudo-second order Mahdavinia et al., 2016
Cd(II) Vermiculite/CTS 2047.0 Langmuir Pseudo-second order Padilla-Ortega et al., 2016
Cd(II) Vermiculite-HDTMA/CTS 1211.0 Langmuir Pseudo-second order Padilla-Ortega et al., 2016
Nd(III) Sepiolite/Sacram 1929.0 Langmuir Pseudo-second order Alcântara et al., 2014b
Pb(II) Sepiolite/CTS 100.0 – – Alcântara et al., 2014a
Cu(II) Sepiolite/CTS 75.0 – – Alcântara et al., 2014a
Pb(II) Palygorskite/ALG 290.0 – – Alcântara et al., 2014a
Cu(II) Palygorskite/ALG 65.0 – – Alcântara et al., 2014a
Cr(VI) Bentonite/ST 4.0 Langmuir Pseudo-second order Koriche et al., 2014
Cr(VI) Mt/CELL 22.2 Langmuir Pseudo-second order Kumar et al., 2012
Pb(II) Bentonite/CTS 26.4 Freundlich Pseudo-second order Futalan et al., 2011
Cr(VI) Mt/CTS 357.1 Langmuir Pseudo-second order Pandey and Mishra, 2011
Pb(II) Mt/ALG 244.6 Langmuir Pseudo-second order Shawky, 2011
Se Mt/CTS 18.4 Langmuir Pseudo-second order Bleiman and Mishael, 2010

ALG: alginate; β-CD: β-Cyclodextrin; CELL: cellulose; CTS: Chitosan; LDH: Layered double hydroxide; Mt.: Montmorichonite; ST: Starch.
Applied Clay Science 198 (2020) 105838
M.d.M. Orta, et al.
clay surfaces. The interaction of some organic cations, like alky-
lammonium cations, with clay minerals can modify the affinity for
anionic pesticides by changing the nature of the clay mineral surfaces
from hydrophilic to hydrophobic or, if adsorbed in excess of the CEC of
the clay, even producing charge reversal. Adsorption of CTS on Mt. with
excess of the CEC of the clay mineral results in structures with good
adsorption properties for anions because the –NH3+ groups not directly
involved in the interaction with the clay surfaces can act as anionic
exchange sites. Along these lines, Celis et al. (2012) synthetized a CTS-
Mt bionanocomposite to be used as an adsorbent of the herbicide clo-
pyralid from aqueous solutions and soil/water suspensions. The CTS-Mt
composite proved to be a useful adsorbent under mild acidic conditions,
that is, when the herbicide is mainly in its anionic form (pKa = 2.3)
and CTS in its cationic form (pKa = 6.3). High NaCl concentrations
promoted the desorption of the adsorbed clopyralid from CTSeMt,
supporting ion exchange as the primary adsorption mechanism.
Amendment with CTS-Mt (5–10%) to acidic soil resulted in an in-
creased clopyralid adsorption, whereas this effect was negligible for
basic soils. Moreover, the presence of easily reversible ad-
sorption–desorption interactions suggests that CTS-Mt-based formula-
tions of pesticides can yield slow release and consequently reduce an-
ionic pesticide mobility into soil and ground and surface water. A ST-
hectorite nanocomposite has also been assessed as adsorbent for di-
camba, an herbicide, from aqueous solutions and the findings show
adsorption to be highly pH-dependent (Pinto et al., 2016) with higher
adsorption observed at pH values of 2.0–4.0 (pH < pHpzc) when the
pesticide (negatively charged) is attracted to the positive surface of the
bionanocomposite via electrostatic interactions. While at pH values of
6.0–11.5, the bionanocomposite surface is negatively charged (pH >
pHpzc), which explains the low herbicide adsorption capacity. More-
over, at pH values above 7.0, competition for the surface of the ST-
hectorite bionanocomposite was observed between the negatively
charged herbicide and OH groups of the medium. The isotherm studies
followed the typical Langmuir behavior. The capacity of this bionano-
composite to adsorb dicamba was 251.9 mg/g, related to a pseudo-
second-order kinetic.
Bionanocomposites have also been applied for the removal of ca-
tionic pesticides from aqueous solutions. Etcheverry et al. (2017) pre-
pared an ALG-Mt nanocomposite for the removal of paraquat, a qua-
ternary ammonium compound widely used as a contact herbicide to
control broad-leaved weeds. The adsorbed paraquat was linearly cor-
related with Mt. content, the maximum adsorption capacities (qmax)
increased from 0.093 to 0.278 mmol/g for Mt. contents from 0.5 to
70%, respectively. The adsorption capacity of ALG is much lower than
Mt., but ALG is also necessary as it acts as a support for clay particles.
As mentioned previously, a sustained release of pesticides into soils
is required for efficient bioavailability and environmental protection.
Recently, Wang et al. (2019) have used an hydrophobic derivative of
sodium ALG, polyacrylamide and Mt. to synthetize stretchy nano-
composite hydrogels with double networks to achieve a slower release
of l-cyhalothrin. They also found that the hydrophobic interactions
between l-cyhalothrin molecules and the hydrophobic groups grafted
on the side chains of sodium ALG have an important role in the loading
efficiency and in the controlled pesticide release. The hydrogel con-
taining 5% Mt. showed the lowest cumulative release percentage of
6.68% over 87 h and the pesticide release profile followed the Weibull
model. These novel materials combine the advantages of ALG deriva-
tives (gelation) and nanoclays (adsorption capacity) to become carriers
for enhancing the distribution efficiency of water-insoluble pesticides.
6.2. Bisphenol A
BPA is a chemical produced in large volumes worldwide. Its main
uses are as a monomer for the synthesis of polycarbonate (~80%) and
epoxy (~18%) resins. These polymers are used as coatings in almost all
food contact materials, in the production of CDs and DVDs, electronic
14
Applied Clay Science 198 (2020) 105838
equipment, medical devices, dental fillings, thermal paper, toys, and
others. There is a large body of research on the adverse effects of BPA
on reproduction and development, neural networks, metabolism, car-
diovascular and immune system in in vitro assays and animal models.
BPA can enter the environment through different pathways such as
wastewater treatment plant effluents, industrial discharge and landfill
leachate (Martín et al., 2019b).
Shabtai and Mishael, 2018synthetized a regenerable sorbent con-
sisting of a polymer of βCD units modified with a cationic group
(pCD+) and Mt. The design of this sorbent allows simultaneous ad-
sorption of BPA (which fills the βCD cavities) and anionic organic
matter (through electrostatic interactions). BPA adsorption was not
affected by the high organic matter adsorption. Most of the works
available on pollutant removal are not conducted using real wastewater
samples, and they only test sorbents in suspension, no by column fil-
tration, and they do not deal with sorbent regeneration. In contrast,
Shabtai and Mishael (2018) used the selective elution of BPA and or-
ganіc matter on the sorbent using alkaline solutions and brine, re-
spectively, to achieve successful in-column regeneration. They also
demonstrated that the removal performance of pCD+–Mt is superior to
that of activated carbon (Shabtai and Mishael, 2018) by assessing the
simultaneous removal of 38 micropollutants, commonly found in
treated wastewater, such as pesticides and pharmaceuticals. The au-
thors found that pCD + -Mt exhibited higher adsorption capacity to-
wards 34 pollutants than activated carbon.
6.3. Hydrophobic organic pollutants
Zhu et al. (2017) evaluated the capacity of Mt. modified with dif-
ferent volumes of HDTMA-Mt and CTS (H/CTS-Mt) to adsorb hydro-
phobic organic contaminants, heavy metals and dyes from water. Mt. is
usually ineffective for the adsorption of hydrophobic organic pollutants
owing to the hydrophilic characteristics of its surface and charges (Zhu
et al., 2017), but HDTMA-Mt can adsorb phenol thanks to the formation
of more effective organic phases (Zhu et al., 2017). After modification
with 2% and 4% CTS, the capacity to adsorb phenol was increased, but
when the amount of CTS was higher than 6%, the adsorption decreased.
The adsorption isotherms followed a partition-dominated mechanism.
These authors suggest that cationic polymers might modify the ar-
rangement of HDTMA (increase in packing density) within the clay,
which in turn would increase the amount of adsorbed hydrophobic
organic contaminants on the OMt. In contrast, an excess of cationic
polymers results in higher packing density of HDTMA, which might
reduce the adsorption of hydrophobic organic contaminants due to
steric hindrance within the interlayer spaces of Mt.
Polychlorinated biphenyls (PCBs) are another example of hydro-
phobic organic pollutants which consist of one to ten chlorine atoms on
two benzene rings. Some PCB congeners do not easily degrade in the
environment and although they are no longer manufactured, they
persist for many years. Barreca et al. (2014) investigated the use of
ALG-Mt beads for the removal of PCBs from aqueous solutions and their
findings revealed that higher initial PBC concentrations and longer
adsorption times improve adsorption. Adsorption of trichlorobiphenyls
on the bionanocomposite followed a Freundlich isotherm model, while
adsorption of tetra-, penta-, and hexachlorobiphenyls were best fitted to
Chapman model. Kinetic followed a pseudo-second order model. By
comparing the adsorption % using the same number of beads (10 beads,
same volumen), best removals were obtained by using hybrid ALGeMt.
6.4. Dyes
Natural clays such as Mt. exhibit weak adsorption capacity of an-
ionic dyes due to the repulsive electrostatic interactions occurring be-
tween the negatively charged surface of the clays and the dye (Wang
and Wang, 2007a, 2007b). The work by Zhu et al. (2017) investigated
the adsorption capacity of Mt. modified with HDTMA and CTS for
M.d.M. Orta, et al.
Congo red (CR) and crystal violet (CV). Both HDTMA-Mt and HDTMA
(60%)/CTS (2%)-Mt showed good adsorption capacity towards CR.
Their results showed an effective adsorption capacity of Mt. and
HDTMA (60%)/CTS (2%)-Mt to CR despite both adsorbents having
negative zeta potential in their surfaces. This suggests that there are
stronger interactions capable of overcoming the repulsive forces be-
tween the dye and the adsorbents. Moreover, it was observed that the
increase in CTS% resulted in higher adsorption capacity of CR due to an
increase in the zeta potential, which is indicative of the role played in
the adsorption process by electrostatic interactions. Similar studies
have reported that high CTS% significantly increases the adsorption of
anionic dyes onto positively charged CTS-Mt (Liu et al., 2013; Wang
and Wang, 2007a, 2007b).
As for CV, their results found good adsorption capacity of Mt. which
can be explained by cation exchange between the dye and the re-
maining Ca2+ on Mt. surface and by the electrostatic interactions be-
tween the negatively charged surface of Mt. and the dye. The hydro-
phobic interactions between HDTMA aggregates and CV might also be
responsible for dye adsorption (Zhu et al., 2017). The adsorption ca-
pacity of HDTMA/CTS-Mt to CV was lower than that of Mt. and
HDTMA-Mt, with higher CTS% resulting in lower adsorption capacity.
This can be explained by the reduced negative charge of Mt. surface
(that can even be reversed to possitive) associated with higher CTS%
and lower Ca2+ remaining on HDTMA/CTS-Mt. Authors also observed
that the co-existing dyes (CR and CV) enhanced the adsorption sites for
phenol probably due to the π-π interaction between them (Zhu et al.,
2014; Wei et al., 2009).
The removal of CR from aqueous solution with cationic ST-bento-
nite was close to 100% compared to 10% removal of pristine bentonite
(Koriche et al., 2013). Ahmad and Mirza. (2018a) evaluated guar gum-
bentonite bionanocomposite for the removal of Pb (II) and CV dye from
wastewater samples and found that the adsorption of both pollutants is
affected by pH, amount of contaminants, contact time and temperature.
The optimal adsorption capacity was observed at pH 5.1 and 7.6,
contact time 240 min and 300 min for Pb(II) and CV, respectively. The
adsorption kinetics followed the pseudo-second order model for both
contaminants which indicates that chemisorption is a rate determining
step and the adsorption isotherm was best fitted to a Freundlich model
for Pb(II) and Langmuir model for CV. They also reported that the
adsorption process was endothermic and spontaneous with increased
randomness at solid-solution interface. In addition, guar gum-bentonite
adsorbent was easily regenerated (reused in five more cycles) with
0.1 M HCl. This bionanocomposite was also used for the removal of
heavy metals from wastewater from various industrial and medical
processes before and after spiking with CV solution. Vinod and
Anirudhan (2003) used humic acid immobilized on modified Mt. by
exchange with polymeric hydroxy cations as adsorbent of the dyes CV,
methylene blue (MB) and rhodamine B from aqueous solution and
found that the adsorption capacity was two-fold higher for the modified
Mt. than for the pristine clay. The adsorption % was concentration
dependent, decreasing with an increase in dye concentration. The ad-
sorption process was pH dependent: maximum adsorption capacities
were found at pH 5.0–7.0. Dyes adsorption was best described by the
Freundlich model. Finally, the authors conducted competitive adsorp-
tion studies to determine the adsorption behavior of each dye from
binary mixtures.
Auta and Hamed, 2014prepared and assessed a CTS-modified ball
clay (MBC) composite that was highly effective for batch and fixed-bed
adsorption of MB. Ball clay has over 70% of kaolin and small amounts
of quartz and other impurities. The adsorption of MB on CTS-MBC in-
creased with dye concentration and pH 4.0–12.0. The adsorption pro-
cess was spontaneous and endothermic. Sulphate anions had greater
inhibition effect than those of sodium chloride and bicarbonate on CTS-
MBC. Lastly, the authors reported that after five regeneration cycles the
adsorption performance was above 50%.
Zubair et al. (2018) used ST-NiFeLDH bionanocomposite (1:1 and
15
Applied Clay Science 198 (2020) 105838
2:1) for the removal of methyl orange (MO) from aqueous phase and
their results showed that dye removal increased when the adsorbent
dosage was increased (from 2 to 10 mg) for 1:1 and 2:1 bionano-
composites probably due to the increase in the number of adsorption
sites. In addition, the removal % decreased when initial MO con-
centration was increased. They reported 99% and 90% removal with
adsorption capacities of 387.59 mg/g and 358.42 mg/g at pH = 3 for
ST-NiFeLDH (1:1) and ST-NiFeLDH (2:1), respectively. The adsorption
kinetics followed a pseudo-second order model. The irregular and
rough surface of ST-NiFe-LDH composites, mentioned in Section 3, re-
sults in an increased number of adsorption sites which in turn increases
the trapping of dye molecules. Recovery of ST-NiFeLDH with little loss
of its adsorption capacity was achieved with NaOH solution. Lastly, the
authors compare the adsorption capacity of the prepared bionano-
composite with other absorbents such as active carbon, graphene, Ni-
FeLDH, MgAlLDH, cork powder and bottom ash, and conclude that ST-
NiFeLDH exhibits optimal capacity for the adsorption of MO.
6.5. Metal ions
Heavy metals are among the most toxic compounds that can enter
the environment. They are not biodegradable and accumulate in the
environment producing toxic effects even at low concentrations
(Ahmad and Mirza (2018a). The United States Environmental Protec-
tion Agency (US EPA) has established the health advisory levels of Pb
(II), Cu(II) and Ni(II) at 0.05 mg/L, 2 mg/L and 0.015 mg/L, respec-
tively (Ahmad and Mirza, 2018a, 2018b, 2018c). The development of
novel bionanocomposites used as adsorbents will play an important role
in the protection against environmental pollution by heavy metals.
Numerous studies have reported on the use of bionanocomposites for
the adsorption of heavy metals such as Pb(II), Cd(II), Ni(II), As(V), Cr
(III) or Cr(VI) as well as their chemically modified derivatives.
Recently, Mukhopadhyay et al. (2020) provided a complete review
of different polymer-clay nanocomposites and their applications in
water remediation. The authors found that some of the individual
limitations of clays and polymers (low specificity, sensitivity to pH and
particle size as well as low wettability) are improved by nanocompo-
sites. In this respect, several authors have investigated the use of bio-
polymers in nanocomposites. For instance, Kumar et al. (2012) assessed
Cr(VI) removal from industrial effluents with clay modified with CELL
and optimized various batch parameters like pH, adsorbent loading,
and adsorption time prior to conducting column experiments in was-
tewater spiked with the metal ions. They reported a maximum ad-
sorption capacity of 22.2 mg/g in accordance with the Langmuir iso-
therm model. The absorption kinetics followed the pseudo-second order
model. The adsorbent could be reused with quantitative recovery for 10
adsorption-desorption cycles with sodium hydroxide. The column stu-
dies were further extended to treat a tannery leather effluent rich in
basic chromium sulfate. Their results showed the high capacity of the
nanocomposite for the removal of Cr(III) (> 95%) from the diluted
effluent sample, with negligible anionic and cationic interferences.
When compared with other adsorbents such as HDMA-Mt, CTS-Mt or
acid activate kaolinite, the prepared bionanocomposite showed a rea-
sonably good adsorption capacity for Cr(III). Pandey and Mishra (2011)
used solution blending for the development of a CTS-Cloisite 10A bio-
nanocomposite for the removal of Cr(VI) from aqueous solution. CTS-
Cloisite 10A takes advantage of the hydrophilicity of the polycationic
polysaccharide and adsorption capacity of inorganic polyanion. Al-
though the adsorption occurs in a wide pH range, pH 3 was the optimal
pH value. Based on the Langmuir model, the maximum adsorption
capacity was 357.14 mg/g. The absorption kinetics followed a pseudo-
second order model. CTS-Mt also showed efficient uptake of As(V) and
Cr(VI) ions, with adsorption capacities of 8.9 mg/g (pH 4–5) and
9.3 mg/g (pH 3.5), respectively (An and Dultz, 2008). Adsorption iso-
therms were fitted to the Langmuir and Dubinin-Radushkevich equa-
tions. The adsorbed ionic species were pH dependent, as did the degree
M.d.M. Orta, et al.
of protonation of the amine groups, and this played a decisive role in
the amount of anions adsorbed. By increasing the concentration of the
competitive anion, Cl-, in solution, the amount of Cr(VI) and As(V)
adsorbed remained almost constant, whereas sulphate anion had a
more pronounced competitive effect. CTS-vermiculite bionanocompo-
site foams were developed by Padilla-Ortega et al. (2016) for the re-
moval of Cd(II). The synthesis of vermiculite-based nanocomposites is
normally complicated because the high charge density per unit cell in
its layers prevents high molecular weight polymers to intercalate be-
tween the vermiculite layers. In order to improve CTS intercalation, the
authors used ultrasound which caused exfoliation of the nanocompo-
sites owing to the high degree of intercalation achieved. The adsorption
capacity of CTS-vermiculite and HDTMA-vermiculite-CTS was three
times higher than the absorption capacity of the pristine vermiculite
and it was increased with incrased pH, which promotes chelation me-
chanisms. Electrostatic interactions, cation exchange and chelation
were the primary mechanism. Azzam et al. (2016) used solution mixing
for the development of a nanocomposite based on CTS and gold and
silver nanoparticles (NPs) for the removal of Cu(II) ions from aqueous
solution. Their results revealed higher Cu(II) adsorption using CTS-
AgNPs-clay and CTS-AuNPs-clay than using CTS-clay composite, which
is indicative of the role played by the metal nanoparticles in the im-
provement of adsorption. The maximum adsorption capacity of CTS-
AgNPs-clay composite was 181.5 mg/g. Lastly, the authors reported
that contact time, Cu(II) initial concentration, adsorbent dose or solu-
tion pH did not have an impact on Cu(II) removal.
In three micro-scale experiments Anirudhan and Suchithra (2010a,
2010b) used a humic acid-immobilized amine-modified poly-
acrylamide–bentonite composite for the removal of heavy metals from
simulated wastewater. The experiments were conducted for de-
termining the removal capacity for specific heavy metals from three
types of synthetic wastewater: (i) Cu(II) removal from wastewater
coming from surface electroplating operations; (ii) Zn(II) from in-
dustrial wastewater; and (iii) Co(II) from water used as coolant in nu-
clear reactors (Anirudhan and Suchithra, 2010b). Their findings
showed the high capacity of low doses of nanocomposite (10 g/L) for
the removal (close to 100%) of the different metals, which suggests the
possibility of applying this modified bentonite for the removal of heavy
metals from actual industrial wastewater. However, paremeters such as
pH and initial concentration of metals should be further investigated.
Ahmad and Mirza (2018b) developed a nanocomposite using mica
modified with XG and n-acetyl cysteine for the removal of Pb(II), Cu(II)
and Ni(II) from aqueous solutions. Their findings showed that higher
temperatures increase the monolayer adsorption capacity and that the
adsorption process is an endothermic and spontaneous reaction occur-
ring more randomly at the solid-solution interface. The adsorption
process followed pseudo-second order model and Langmuir adsorption
isotherm with 530.54, 177.2 and 51.48 mg/g for Pb(II), Cu(II) and Ni
(II), respectively, at pH values 4–5 and contact time between 1 and 2 h.
The adsorbent was easily regenerated with HCl for all metal ions. The
same authors also developed a recyclable XG-Mt for the removal of Pb
(II) from synthetic and industrial wastewater. The kinetic study re-
vealed that the adsorption process of Pb(II) followed the pseudo-second
order model, confirming chemisorption. The adsorption isotherm was
consistent with the Freundlich model for Pb(II). Thermodynamic stu-
dies showed that absorption was driven by a physisorption process that
was spontaneous and endothermic with increased randomness. The
bionanocomposite was easily regenerated for five more cycles with
0.05 M HCl and incinerated when exhaust, which suggests that this XG-
based nanocomposite might be an inexpensive potential adsorbent for
actual wastewater treatments.
Li et al. (2018) used a CTS-LDH bionanocomposite for the removal
of selenate and selenite oxoanion and reported higher removal of Se(VI)
with CTS-LDH (> 80%) than with CTS (57%) due to the increased
adsorption provided by LDH incorporation. The maximum adsorption
capacities from Langmuir isotherms were 17 mg/g for Se(IV) and
16
Applied Clay Science 198 (2020) 105838
~12 mg/g for Se(VI) which are higher than the capacities obtained with
CTS embedded with other nanocrystalline metal oxide fillers. Alcântara
et al. (2014b) investigated the properties of a recently discovered
polysaccharide called sacran, extracted from fresh water algae, which
can modify sepiolite fibers to form a biosorbent used for the uptake of
lanthanide ions from aqueous solutions. The authors reported that the
orientation of the sacran chains as liquid crystals can be controlled by
modifying sacran % in the bionanocomposite and by the preparation
method. This liquid crystal arrangement seems to be responsible for the
higher adsorption capacity and selectivity for Nd(III) ions compared to
Ce(III), Eu(III) and Gd(III) lanthanides. Bionanocomposites prepared
using sacran solutions (> 0.5%, w/v) with sepiolite (43%, w/w) showed
a maximum adsorption of 13.4 mmol/g for Nd(III). Lastly, the authors
suggest that the preservation of the self-orientation of sacran chains in
the liquid crystalline state after assembling with the sepiolite fibers is
responsible for the enhanced adsorption.
7. Conclusion and future potential
Nanoscale assembly of biopolymers on clay minerals for bionano-
composite formation has allowed the development of ecofriendly
functionalized adsorbents that are considered a promising approach in
water remediation. In the last decade, different biopolymer-clay na-
nocomposites having similar to or higher adsorption capacity than
commercial adsorbents have been developed. The clays can be modified
to enhance their properties and dispersion within the polymer matrix.
The most commonly used biopolymers are the polysaccaharides CTS,
CELL, ST, ALG and CD. The resulting properties will be determined by
the modification method and the agent used for clay functіonalіzation.
In this respect, solution blending seems to adequately enhance the
dispersіon of the clay within the matrіx.
The control of the interactіons between biopolymer and clay will
allow the creation of smart nanomaterials with exceptional properties
like thermal stability and hydrophobic surface, which will widen the
number of environmental applications. Many authors have expressed
the necessity to further investigate the role played by contact tіme,
іnіtіal polymer concentration, polymer/clay ratio and the nature of the
clay in the optimization of the polymer loadіng. The main factor in-
fluencing the optimization is the nature of the clay as the presence of
electrostatic attraction enhances the adsorption capacity. In addition,
the presence of magnetіc nanoparticles in the polymer matrіx can also
optimize the functionality of bionanocomposites. Thіs review opens up
the possibility of exploring novel biopolymers that will allow the im-
provement of nanocomposites to act as adsorbents of environmental
pollutants.
The adsorption capacity of these bionanocomposites for the removal
of different classes of organic contaminants, emerging pollutants, and
inorganic heavy metals from water has been tested at laboratory scale.
However, the application of these nanocomposites as adsorbents in
industrial and environmental settings is still in the research stage. Most
of the experіments have been conducted using synthetic contaminated
water (obtained by dissolution of pollutants in deionized water) and
previously established experimental conditions. However, settings with
actual contaminated water are complex systems in which a diverse
collection of biological and interference species and organic compo-
nents can be present in large amounts. After our literature review, we
have found no full-scale experiment on the use of bionanocomposites
for environmental remediation. In order to be able to conduct full-scale
experiments, a deep understandіng of the structural stability of biona-
nocomposites and their environmental toxicity is paramount to de-
monstrate their practical applications.
In addition, few studies have addressed the regeneration capacity of
biopolymer-clay-based adsorbents, which allows the reduction of the
amount of waste generated and the removal of bulk amounts of con-
taminants. In this regard, these affordable clay mіnerals can be suc-
cessfully used in regeneratіon studies. Financial analyses would also
M.d.M. Orta, et al.
help to understand the feasibility and durability of these adsorbents at
ground level as there is little financial information on the sustainable
use of bionanocomposites for water remediation. In this respect, the
utilization of naturally occuring clay mіnerals will help to reduce the
production costs.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This work was supported by the Spanish Ministry of Economy,
Industry and Competitiveness (Project No. CTM2017-82778-R).
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