Uamerica 2024 - 10

Environmental Research 255 (2024) 119089
Contents lists available at ScienceDirect
Environmental Research
journal homepage: www.elsevier.com/locate/envres
Bio-based composite from chitosan waste and clay for effective removal of
Congo red dye from contaminated water: Experimental studies and
theoretical insights
Mouhsine Bellaj a, Aicha Naboulsi b, Khalid Aziz c, Abdelmajid Regti b, Mamoune El Himri b,
Mohammadine El Haddad b, Mounir El Achaby c, Abdelkrim Abourriche a, Lhoucine Gebrati a, d,
Tonni Agustiono Kurniawan e, *, Faissal Aziz f, g, **
a
Laboratory of Materials, Process, Environment, and Quality (LMPEQ), ENSA Safi, Morocco
b
Laboratory of Analytical and Molecular Chemistry, Faculty Poly-disciplinary of Safi, BP 4162, Safi, 46 000, Morocco
c
Materials Science, Energy and Nano-Engineering (MSN) Department, Mohammed VI Polytechnic University (UM6P), Lot 660 – Hay Moulay Rachid, 43150, Benguerir,
Morocco
d
Biochemistry Laboratory, Faculty of Medicine and Pharmacy of Marrakech, Cadi Ayyad University, B.P. 7010, 40000, Marrakech, Morocco
e
College of Environment and Ecology, Xiamen University, Fujian Province, Xiamen, 361102, China
f
Laboratory of Water, Biodiversity Climate Changes, Semlalia Faculty of Sciences, B.P. 2390, 40000, Marrakech, Morocco
g
National Centre for Research and Study on Water and Energy (CNEREE), University Cadi Ayyad, Marrakech, Morocco
A R T I C L E I N F O A B S T R A C T
Keywords: Water pollution due to dyes in the textile industry is a serious environmental problem. During the finishing stage,
Adsorption Congo red (CR) dye, water-soluble, is released into wastewater, polluting the water body. This study explores the
Congo red effectiveness of utilizing a composite composed of Safi raw clay and chitosan to remove an anionic dye from
Composite
synthetic wastewater. The chitosan was extracted from crab shells. Its removal performance was compared to
Density functional theory
Textile wastewater
that of natural clay. Both the composite and raw clay were used to remove target pollutant. The effects of the
chitosan load in the composite, size particles, initial dye concentration, contact time, pH, and temperature on the
dye’s elimination were tested in batch modes. The composite with 30% (w/w) of chitosan exhibited the highest
dye removal. At pH 2, an adsorption capacity of 84.74 mg/g was achieved, indicating that the grafting of the
polymer onto clay surface enhances its efficacity and stability in acidic environments. This finding was supported
by characterization data obtained from X-ray diffraction (XRD), scanning electron microscopy (SEM), dispersive
X-ray spectroscopy (EDX), and Fourier transform infrared (FT-IR) analyses. Under optimized conditions of 20 mg
dose, pH 2, 30 min of reaction time, and 20 mg/L of dye concentration, about 92% of dye removal was achieved.
The Langmuir isotherm model represents dye adsorption by the composite, while dye removal was controlled by
pseudo-second-order model. Thermodynamic data of the adsorption (ΔH = +8.82 kJ/mol; ΔG <0) suggested
that the dye adsorption was spontaneous and endothermic. The findings provide insights into the dye elimination
by the adsorbent, indicating that the removal occurred via attractive colombic forces, as confirmed by density
functional theory (DFT) analysis. Overall, the composite of natural clays and chitosan waste is a promising and
innovative adsorbent for treating wastewater containing recalcitrant dyes.
1. Introduction such as dyes, detergents, bleaches, and heavy metals that can harm
aquatic life, soil quality, and public health. Textile dyeing and finishing
Textile wastewater is a key contributor to global water pollution, account for 20% of industrial water pollution globally (Kurniawan et al.,
posing a serious environmental challenge that affects millions world 2011; Kiani et al., 2021; Hashemi et al., 2022). Moreover, textile
wide (Kurniawan et al., 2010). Textile wastewater contains chemicals wastewater is often discharged without proper treatment, especially in
* Corresponding author.
** Corresponding author. Laboratory of Water, Biodiversity Climate Changes, Semlalia Faculty of Sciences, B.P. 2390, 40000, Marrakech, Morocco
E-mail addresses: [email protected] (T.A. Kurniawan), [email protected] (F. Aziz).
https://doi.org/10.1016/j.envres.2024.119089
Received 19 April 2024; Received in revised form 2 May 2024; Accepted 5 May 2024
Available online 22 May 2024
0013-9351/© 2024 Elsevier Inc. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
M. Bellaj et al. Environmental Research 255 (2024) 119089
developing countries with poorly enforced environmental regulations. wastewater treatment reduces the demand for virgin resources and
This seriously threatens the availability and quality of freshwater re minimizes the generation of additional waste (Fu et al., 2017). This
sources and the sustainability of the textile industry itself (Soon and promotes resource efficiency and environmental protection, while sup
Hameed, 2011). Hence, it becomes imperative to explore solutions for porting a transition towards a circular economy where materials are
eliminating chemical substances from the aquatic environment (Aziz reused and recycled rather than disposed of after a single use. Addi
et al., 2023a; Gebrati et al., 2010, 2011). tionally, the incorporation of clay into the composite material enhances
Many techniques have been tested to treat wastewater laden with its adsorption capacity and provides additional binding sites for target
refractory pollutants, such as adsorption, advanced oxidation processes dye. This synergistic combination of chitosan waste and clay represents
(AOP), ion exchange, photodegradation, chemical precipitation, mem a novel approach to enhancing the efficiency of dye removal from
brane separation, and electrochemical conversion (Chan et al., 2007; contaminated water (Zhu et al., 2022).
Vilve et al., 2010; Rabiee et al., 2022; Mountassir et al., 2012; Lissa Furthermore, the composite utilizes waste material such as chitosan
neddine et al., 2022a; Sarode et al., 2019; Abdoallahzadeh et al., 2023). from crab shells, diverting them from landfills or incineration, which
Among them, granular activated carbon (GAC) adsorption is widely can release greenhouse gases (GHG) like CH4 and CO2. By repurposing
utilized due to its flexibility, high performance, efficient regeneration, the waste materials for composite, this work contributes to waste
and convenient operation (Aziz et al. 2023b; Haydari et al., 2022; Lis reduction efforts and minimizes GHG emissions related to waste
saneddine et al., 2022b; Naboulsi et al., 2024). However, GAC remains disposal. If the composite proves to be more energy-efficient in water
costly, potentially posing a challenge to its widespread adoption in treatment, this can indirectly contribute to reducing energy consump
wastewater treatment. While GAC remains a feasible solution for tion and associated GHG emissions if the material requires less energy to
removing contaminants from wastewater, its cost may restrict its usage produce the composite (Fu et al., 2019).
or necessitate the exploration of alternative cost-effective options in the Additionally, the composite offers an eco-friendly option to con
wastewater treatment domain. ventional water treatment methods that involve hazardous chemicals.
To replace the costly GAC, the search for non-conventional materials Utilizing the composite can lower production costs, as compared to
from natural sources and fishery waste, such as clinoptilolite, clay, and traditional water treatment methods that rely on costly resources. This
chitosan, has intensified in recent years (Kurniawan et al., 2023a). Due makes the technology more accessible for communities with limited
to its lamellar structure, which offers vast specific surfaces, clay exhibits resources. Using natural adsorbents and processes, the composite min
a high adsorption capacity, driven by its natural adsorbent property, imizes its environmental footprint, while reducing environmental
versatility, cost-effectiveness, low environmental impact, selective pollution and minimizing the impact of harmful substances on ecosys
adsorption capabilities, and long-term stability (Ullah et al., 2021). This tems and public health (Kurniawan et al., 2024a).
allows them to effectively retain ions and polar organic molecules on the The inclusion of theoretical investigations in this work adds depth to
external sites of clay particles and in the interlayer positions. This dual the study by providing insights into the underlying mechanisms gov
adsorption capacity contributes to their efficiency in the adsorption erning the adsorption process of target dye by the adsorbent. Under
(Premakumara et al., 2014). standing the interactions between the composite material and the dye
The process of adsorption and desorption of organic molecules in molecules at molecular level enables a more comprehensive analysis of
clays is primarily influenced by two key factors: the surface properties of its adsorption behavior and aids in optimizing the design of future ad
the clay and the chemical properties of the molecules (Gebrati et al., sorbents for wastewater treatment applications. Through a combination
2010). In this case, its adsorption capacity is influenced by the clay’s of experimental studies and theoretical insights, this study not only
surface characteristics and the nature of the target organic molecules. demonstrates the practical viability of the composite, but also contrib
Additionally, the raw clays possess a negative structural charge, utes to advancing our understanding of adsorption processes for
enabling them to effectively adsorb positively charged dyes (Aziz et al., wastewater treatment (Lo et al., 2009).
2017; Gebrati et al., 2011). However, due to this negative charge, their To reflect its novelty, this study investigates the applicability of Safi
adsorption capacity for anionic dyes is low. To improve its adsorptive raw clay and chitosan waste-based composite to eliminate Congo red
properties for target pollutants, clay need to be modified physico dye from synthetic wastewater. For this purpose, a composite was syn
chemically into a composite-based adsorbent by integrating it with thesized based on integrated clay and chitosan and characterized using
chitosan as a hybrid material (Khandamov et al., 2024). XRD, SEM, EDX, and FTIR. The effects of the chitosan’s load in the
Chitosan is a biopolymer derived from the deacetylation of chitin. It composite, particle size initial dye concentration, pH, contact time, and
is the main component of the exoskeletons of crustaceans and insects temperature on the dye’s removal were tested in batch modes. The
with –OH and –NH2 functional groups (Wu et al., 2001; Binaeian et al., observed data were adjusted using various isotherm models (Langmuir,
2020; Azari et al., 2022). Chitosan can be obtained from fishery waste, Freundlich, and Temkin). In addition, the thermodynamic and kinetic
such as crab shells, which are usually discarded or incinerated, causing study of dye adsorption by the composite was made to understand the
environmental problems and economic losses (Bellaj et al., 2024a; mechanism of dye elimination by the composite. Hence, DFT functions
2024b). Transforming the fishery waste into chitosan generates a valu as a potent computational tool in investigating the elimination of Congo
able resource, reducing the environmental footprint of the seafood red dye by a composite made of chitosan and clay. This offers a
sector. Through the utilization of chitosan waste - a residual product of comprehensive understanding of molecular interactions, energetics,
diverse industries like seafood processing-as an adsorbent, this work structural alterations, and electronic properties pertinent to adsorption.
presents a sustainable remedy. This approach not only diminishes waste This work is expected to be extended to other pollutants using the
but also maximizes the utilization of an easily accessible resource. same composite. The composite’s versatility enhances its practicality for
Consequently, it amplifies the composite’s capacity to sequester and addressing a wide range of water quality issues beyond the model
adhere to target contaminants (Batool et al., 2023a). pollutant studied. This study also provides valuable insights that can
The novelty of the eco-friendly composite made from clay-chitosan facilitate future work and development efforts by exploring the in
waste for eliminating Congo red dye from contaminated water not teractions between the composite and the dye at both experimental and
only reflects the UN SDG#12 ‘Sustainable Production and Consump theoretical levels (Kurniawan et al., 2024b). Last, but not least, this work
tion’, but also lies in its innovative approach to addressing water promotes sustainable practices that concern climate resilience by
contamination issues through the development and utilization of a bio- demonstrating the technical feasibility of using eco-friendly composite
based composite material. This work adds value to the unused waste by for wastewater treatment. This can inspire a broader adoption of green
repurposing it for environmental remediation, thereby reducing waste technologies and contribute to a shift towards sustainable water man
and promoting sustainability. Repurposing waste materials for agement practices globally.
2
2. Materials and methods
2.1. Materials
Chemicals and reagents were analytical grades and utilized as

received without further purification. C2H4O2 (≥99.0%), HCl (37%),
and NaOH (99%) were acquired from Sigma Aldrich (Rabat, Morocco).
In its raw form, clay was sourced from a mine in Safi. Drying, rinsing,
and grinding were performed on the collected sample.
Congo red (CR) dye used in this study was supplied by Sigma-Aldrich
(Rabat, Morocco). Its chemical structure and properties are presented in
Table 1.
The UV–visible spectra of congo red depicting three solutions pre
pared in different media are presented in Fig. 1. The solutions comprised
50 mg/L of the dye. This work aimed to ascertain the dye’s wavelengths
in various media. The identical nature of the results from the three
curves suggests that the pH influences the wavelengths of Congo red.
Within the visible range (400–800 nm), a distinctive wavelength of the
dye was identified in each medium: 564 nm for the acidic medium, 518 Fig. 1. UV-VIS spectra of Congo red dye with 50 mg/L of concentration in
nm for the basic medium, and 498 nm for the neutral medium. neutral, basic, and acid media.
2.2. Methods analyzed using a combination of scanning electron microscopy (MEB)

and energy-dispersive X-ray spectroscopy (EDX). The TESCAN VEGA 3
2.2.1. Chitosan synthesis model (Tokyo, Japan) was used for this purpose. MEB provides high-
Chitosan was obtained through a series of steps that included resolution images of the sample surface, while EDX detected and
cleaning, demineralization, deproteinization, and deacetylation, ulti quantified the elements present in the sample by analyzing the charac
mately resulting in the isolation of chitosan as the final product (Fig. 2), teristic X-rays emitted when the sample was bombarded with electrons.
and the degree of deacetylation was measured by a direct assay method. A T60 UV–Vis spectrophotometer was employed to determine the
It was found to be 70%. remaining concentration of Congo red after adsorption. UV–Vis spec
The raw Safi City clay from Morocco was initially ground into a troscopy measured the absorption of ultraviolet and visible light in the
powder using a crusher with a 45 μm sieve, forming a base material for a solution, allowing for the quantification of a particular substance based
specific composite. To form a composite, 2.33 g of the finely ground clay on absorption characteristics.
was dispersed in 50 mL of distilled water with continuous agitation for 4
h. Meanwhile, chitosan was dissolved in 1 M acetic acid and combined 2.2.3. Batch adsorption study
with the dispersed clay under a constant stirring for 48 h. Then, 50 mL of In the batch experiment, the adsorption was studied in a closed
0.5 M NaOH was added and continuously mixed for 12 h. Subsequent reactor where the clay-chitosan composite and Congo red dye were
steps involved washing the composite with distilled water and neutral brought into contact and allowed to interact. To prepare 100 mg/L of
izing it to achieve a pH ranging from 6 to 7. Finally, the composite was anionic dye stock solution, a predetermined amount of Congo red dye
subjected to drying for 12 h in an oven set at 60 ◦ C. was dissolved in 1 L of deionized water. This stock solution served as the
source of congo red dye for this study.
2.2.2. Characterization of adsorbent A 50 mL solution of Congo red dye was prepared from the stock
X-ray diffraction (XRD) was employed to determine the crystal solution with an initial concentration of 20 mg/L. This concentration
phases present in the samples. The Rigaku Smart Lab diffractometer, was lower than that of the stock solution to prevent saturation of the
equipped with a Cu anode emitting X-rays with a wavelength of 1.5418 adsorption at the experiment’s outset. The pH of the synthetic waste
Å, was utilized for this purpose. XRD measured the diffraction pattern water was adjusted to a predetermined value.
produced when X-rays interacted with a material’s crystal lattice, Furthermore, the experiment was conducted under ambient tem
providing information about its crystal structure and phase composition. perature, as temperature impacted adsorption kinetics and equilibrium.
Fourier-transform infrared (FT-IR) spectroscopy was utilized to identify At ambient temperature, the variation of temperature was controlled
functional groups on the surface of the samples within the spectral range while optimizing pertinent parameters. The dose of adsorbent was var
of 4000–400 cm− 1(Batool et al., 2024). The VERTEX 70 FT-IR spec ied from 10 to 60 mg, while reaction time was varied from 10 to 60 min.
trometer (Tokyo, Japan) was applied for this analysis. Subsequently, solution pH was varied from pH 2 to 12; while initial
FT-IR spectroscopy measures the absorption of infrared light by Congo red concentration was varied from 10 to 40 mg/L. Only optimum
chemical bonds in a material, allowing for the identification of func parameter was used for subsequent batch studies.
tional groups present based on their characteristic absorption fre All adsorption tests were carried out at 600 rpm of agitation speed.
quencies. Material atomic element content and surface images were Subsequently, the suspensions were centrifuged using a centrifuge. The
Table 1
Characteristics of Congo red dye.
Dye Chemical structure Type CI Number Molecular weight (g/mol) ƛmax (nm)
Congo red (CR) Azo 22120 696,665 g/mol Neutral 498

Acidic 564 Alkaline 518
3
Fig. 2. (a) Chitosan extraction from crab shells; (b) Synthesizing composite from clay and chitosan.
remaining dye concentration in the supernatant was analyzed using a 3. Results and discussions
UV–Vis spectrometer in a neutral environment (λmax = 498 nm), an
acidic environment (λ max = 564 nm), and a basic environment (λmax = 3.1. Composite characterization
518 nm) (Zhu et al., 2023). To determine the remaining dye concen
tration in the solution and the amount of dye sorbed by the adsorbent, Figure (3-a) shows chitosan, raw clay, and composite XRD spectra.
Equation (1) was utilized: As a semicrystalline polymer with a unique crystal structure, chitosan
( ) had a strong diffraction peak at 20.07◦ wavelengths (Abdeen, 2016).
R%
Ce = C0 × 1 − (1) Based on the previous analysis of the raw clay sample, the main minerals
100
detected included illite K0.5(AlFeMg)3(SiAl)4O10(OH)2, kaolinite
(Al2Si2O5(OH)4), dolomite (CaMg(CO3)2), calcite (CaCO3), and quartz
where: Ce is the final dye concentration in the solution at equilibrium
(SiO2) (Kurniawan et al., 2023d). The composite’s diffraction peaks
(mg/L), C0 is the initial concentration of the Congo red dye solution
followed the same pattern as raw clay in the XRD spectrum. The crystal
(mg/L), and R% represents the dye’s removal efficiency.
structure of the composite was the same as that of clay, which indicated
To calculate the amount of dye sorbed by the adsorbent based on the
that the chitosan was well-grafted into the composite. Changes in
difference between the initial and equilibrium concentrations, Equation
diffraction peaks following the adsorption process were investigated
(2) was used to calculate the equilibrium concentration of the dye in the
through X-ray diffraction (XRD) analysis. Shifts toward lower angles
solution.
were also observed, indicating an interaction between the composite
V and the adsorbate. Notably, a reduction in the width of the peaks was
qe = (C0 − Ce ) × (2)
m obvious, implying crystalline disorganization due to its interaction with
the dye (Kurniawan et al., 2024b).
where: qe is the amount of dye sorbed by the adsorbent (mg/g), while V
The FT-IR spectra obtained for chitosan and the composite before
is the volume of the dye solution (mL), and m is the mass of the com
and after dye adsorption are presented in Figure (3-b). The broad bands
posite (mg).
appeared at 3300–3570 cm− 1, corresponding with –OH and –NH
stretching vibrations during the adsorption (Crini and Badot, 2008; Gu
et al., 2023; Hashemi et al., 2023). On the glucopyranose cycle of the
chitosan, the peak at 2915 cm− 1 represented the absorption of stretching
vibrations of –CH2 and –CH3. At 1666 cm− 1, the Class I amide band
peaks appeared, while the low amino group (-NH2) band appeared at
4
Fig. 3. (a) XRD analysis of raw clay material and its composite before and after Congo Red removal; (b) FT-IR spectra of raw clay material and its composite before
and after Congo Red removal.
1600 cm− 1. The band at 1378 cm− 1 showed -COH vibrations in the surface of the clay-chitosan composite, a distinct shift of the peaks in the
chitosan’s structure (Kousalya et al., 2010). This might be due to the FT-IR spectra towards lower wavelengths became evident. This shift
distortion of the O–H and N–H bands because of the interaction between indicates specific interactions between the adsorbate and the composite.
the functional groups of the dye. Stretching vibrations corresponding to The appearance and adsorption of new peaks and a variation in the in
the –OH groups coordinated with the octahedral cations were observed tensity of existing peaks implied active interactions between target
at 3696, 3668, and 3653 cm− 1 (Khan et al., 2021). The bond charac pollutant and the composite (Hashemi et al., 2023).
terized Si–O bands at 1030 cm− 1 (Jin et al., 2014), and the Si–O–Al bond The Scanning Electron Microscopy (SEM) analysis conducted on the
produced a band between 475 and 748 cm − 1 and at 778.4 cm− 1 (Jin clay-chitosan composite is illustrated in Fig. 4. In Fig. 4-A, the surface of
et al., 2014). The FT-IR spectra of the CR dye-absorbed composite the Safi zone clay was characterized as robust and permeable, while
revealed a slight decrease in its peak intensity and absorbance, implying Fig. 4-B depicts the morphology of the composite after chitosan grafting
the involvement of surface functional groups during adsorption. with irregular folds. This alteration suggests the incorporation of chi
By integrating chitosan into the composite, the spectra obtained tosan into the clay framework (Crini and Badot, 2008).
revealed new materials from various functional groups related to the The SEM analysis reveals an augmentation in clay porosity and
raw clay and chitosan. This confirms that chitosan was well grafted on surface roughness, indicating an elevation in active sites with amine and
the clay’s surface in the composite. After Congo red adsorption on the –OH groups. This success was attributed to the impregnation of the
Fig. 4. SEM image of clay (A), Clay-chitosan adsorbent before (B) and after elimination of Congo red (C). EDX of the composite surface before adsorption (D) and
after Congo red adsorption (E).
5
polymer chains between the clay layers. In Fig. 4-C, post-Congo red
adsorption, a substantial presence of anionic dye molecules was found
on the adsorbent’s surface. The adsorption capacity of the composite
was enhanced by the functional groups introduced by chitosan. The
alterations to the surface post-adsorption provided compelling evidence
of the successful Congo red adsorption by the composite. This affirms
that the composite removed the dye from wastewater. Hence, the
composite’s morphology showed the introduction of functional groups
by chitosan (Sara et al., 2023).
The EDX analysis provided information on the sample’s elemental
composition (Fig. 4-D and 4-E) before and after the dye adsorption. The
composite elements (C, O, Mg, Al, Si, K, Na, and Fe) were identified
based on their original composition and the grafting of chitosan onto the
raw clay (Table 2). A marginal increase in the C atom fraction was
obvious after adsorption. Minor variations were observed in the fraction
of O and Si, the key components. Obvious changes included a decrease in
Mg and an increase in Al after dye adsorption. The existence of S, Na,
and K was detected after adsorption, indicating their incorporation
during the adsorption process. The emergence of the additional elements Fig. 5. pHf = f(pHi) was generated for the composite
implies the adsorption of anionic dye onto the composite during the (Remarks: The intercepts of the plots provide the pHpzc for the adsorbent at
adsorption (Khan et al., 2021). ambient temperature).
3.1.1. Zero-point charge (ZPC) surface area of clay for dye removal, overcoming the limited surface area
The adsorption capacity is induced by the charge density on the of chitosan (Bellaj et al., 2024a; 2024b). Its low crystallinity fraction and
adsorbent’s surface. Fig. 5 displays the carrier’s zero charge point at specific surface area reflected the difference in adsorption capacity be
which the composite’s surface was neutrally charged. At pHzpc = 4.36, tween composite and chitosan alone. As the integration of chitosan and
the adsorption’s carrier surface turned neutral. The presence of cationic clay reduced its crystallinity and increased the specific surface of the
species was encouraged by the negatively charged surface, resulting carrier, this enhanced the probability of exposure of chitosan’s active
from the solution’s higher pH than the pHzpc. When the pH of the so sites to the target dye (Amjad et al., 2024).
lution was lower than the pHzpc, the composite’s surface became satu
rated with H+, resulting in a surface abundant with H+ and facilitating 3.2.2. Impact of contact time and initial dye concentration on Congo red
the adsorption of anionic dye (Fiol and Villaescusa, 2009). Therefore, elimination
the protonation of the –NH2 amine group of the polymer grafting onto The influence of contact time and initial concentration on congo red
the clay surface enhanced the elimination of the anionic dye (Al-Hazmi elimination was tested by varying its initial concentrations from 10 to
et al., 2024). 40 mg/L in 50 mL of synthetic wastewater. A composite dose of 20 mg,
pH 6.5, stirring speed at 600 rpm, and a contact time of 1 h were
3.2. Batch adsorption study maintained throughout the tests. Under optimum conditions, approxi
mately 80% of congo red removal was achieved at an initial dye con
3.2.1. Effects of dose on dye removal centration of 20 mg/L.
The dye removal evaluation involved using various composites such The initial adsorption rate of Congo red within the first 20 min was
as Cs100, CS80, Cs60, Cs50, Cs30, Cs20, and Cs0. They were labeled to significantly high due to the abundant presence of active amine and
indicate the fraction of chitosan in each sample concerning its weight hydroxyl sites on the surface of the composite. These functional groups
(w/w). The primary objective was to identify the most effective adsor could attract and retain the anionic dye molecules through attractive
bent in terms of adsorption capacity for eliminating Congo red dye. A electrostatic interactions. The amine and hydroxyl functional groups
decrease in the amount of chitosan within the composites corresponded exhibited a strong affinity for the dye, leading to a rapid adsorption of
to a decrease in dye removal (Fu et al., 2023). target pollutant (Kurniawan et al., 2023b).
Notably, the composite with 30% (w/w) chitosan and 70% (w/w) Following this initial phase, the adsorption rate gradually slowed
clay demonstrated the highest capability for removing the target dye down and reached an equilibrium plateau after 35 min of physico-
(Figure (6-a)). The adsorbent’s dose affects the dye’s removal. Despite chemical interaction between the composite and the Congo red in the
the raw clay did not adsorb the target dye, dye adsorption was obvious solution. At this stage, about 80% of dye elimination was attained for an
when the composite was used. The adsorption capacity of the composite initial 20 mg/L concentration. This plateau indicated a dynamic equi
was greater than that of individual chitosan and raw clay because as- librium state being reached, where the rate of anionic dye adsorption
received chitosan was more crystalline than cross-linked chitosan. This was counterbalanced by the rate of Congo red desorption (Mokhtar
provided limited access to internal sorption sites for dye removal, et al., 2020). The reaching of the plateau after a long time was likely
resulting in a low adsorption capacity (Mahmoudian et al., 2020; Zahir attributable to the saturation of active sites present on the surface of the
et al., 2017). composite.
The composite reduced the crystallinity of chitosan, as confirmed by When all active sites on the adsorbent’s surface became occupied by
XRD analyses. Consequently, grafting the polymer-rich in amine and dye molecules, the adsorption rate leveled, as there were no further
hydroxyl groups proved beneficial in leveraging the extensive specific available sites to adsorb additional Congo red dye molecules. This
Table 2
EDX analysis (b) before adsorption and (c) after adsorption by composite.
Element weight (%) C N O Si Mg Al S Na K Fe
Before adsorption 5.10 1.91 42.57 24.35 2.23 12.90 – – 5.50 5.44
After adsorption 6.09 1.91 42.68 24.03 1.47 15.04 0.53 0.22 4.66 3.37
6
Fig. 6. Effect of chitosan loading in the composite (a); Effects of dose on dye adsorption (b).
implies that the maximum adsorption capacity of the adsorbent was role in the CR removal. Adsorption tests were conducted at pH 6.5, with
reached, and no further dye was adsorbed on the composite’s surface. a dye concentration of 20 mg/L, and at 20 ◦ C for 1 h, using various
Therefore, the adsorption kinetics was constant, as there was no change biomass particle sizes from 45 to 200 μm.
in the number of adsorbed dyes. Additionally, dye molecules might be Fig. 8-a reveals that the adsorption capacity decreases as the particle
trapped inside the pores of the composite, contributing to their size increases. Larger particles exhibited increased resistance to mass
decreased adsorption rate. This explained why the dye removal did not transfer diffusion, whereas smaller particles enabled rapid adsorption
increase beyond the plateau with a longer reaction time (Kurniawan kinetics if adsorption was primarily a surface phenomenon. The increase
et al., 2024b). in available surface area was attributed to the smaller particle size,
According to Fig. 7-b, an increase in the Congo red dye concentration resulting in a higher adsorbent surface area (Robinson et al., 2002). This
increased adsorption capacity. A dye adsorption capacity of 56.7 mg/g increased surface area provided additional sites for dye molecules to
was recorded when its concentration was 40 mg/L. This could be attach to the composite. Based on Fig. 8-b, composite particles with 45
attributed to the competition among dye molecules for the active sites of μm of size had superior adsorption capacity, as compared to the other
the adsorbent, facilitated by the mass transfer of the anionic dye to the three for CR adsorption.
amine and hydroxyl sites grafted onto the composite’s surface. As a
result, there was an overall enhancement in its adsorption capacity. 3.2.4. Influence of pH on dye adsorption
This result suggests that the initial dye concentration played a role in The pH of the solution plays a crucial role in the composite’s
determining the adsorption kinetics, while the ultimate equilibrium adsorption of Congo red dye. A composite’s surface structure and
state was reached. Not only was it responsible for governing the initial loading are influenced by pH, which controls dye adsorption. Fig. 9 il
rate of adsorption, but it also influenced the rate at which equilibrium lustrates the correlation between dye removal and solution pH.
was achieved. These findings brought significant implications for At acidic pH, the –NH2 group on the surface of the composite were
designing and optimizing processes in removing CR dye and other azoic protonated (Zhao et al., 2021). This protonation modified the surface’s
anionic dyes from wastewater. chemical properties, rendering it favorable for dye adsorption. Through
the protonation of the functional groups, the composite demonstrated an
3.2.3. Particle size’s effects on dye adsorption increased affinity for the anionic dye, resulting in a higher dye removal
According to Fig. 8-a, the particle size of the composite played a key under acidic conditions. This resulted in the formation of positively
Fig. 7. Impact of initial dye concentration and adsorption capacity on the Congo red dye elimination.
7
Fig. 8. Particle size affects dye removal

(Experimental conditions: 0.4 g/L of dose, pH 6.5, 600 rpm of shaking speed, 1 h of adsorption reaction).
diminished the electrostatic attraction between the composite and dye

molecules, reducing adsorption capacity and efficiency. Moreover, at
higher pH levels, the presence of OH− in the solution might compete
with dye molecules for adsorption sites, further diminishing the overall
adsorption capacity.
3.2.5. Effects of temperature on dye removal

Temperature plays a crucial role in determining the adsorption
process’s nature, whether heat is released (exothermic) or absorbed
(endothermic). This information is vital to understand the thermody
namics of the adsorption process. The influence of this parameter on
Congo red dye removal was investigated by conducting experiments at
various temperatures ranging from 298 to 328 K (Fig. 10).
This broad temperature range facilitated a comprehensive analysis of
the impact of temperature on the adsorption of dye by the composite.
Throughout the temperature study, consistent experimental conditions
were maintained to understand the effects of temperature. These con
ditions included maintaining a dose of 20 mg, dye concentration of 20
mg/L, reaction time of 1 h, and an agitation speed of 600 rpm. By
varying the temperature, while keeping other parameters remain con
Fig. 9. Congo red dye removal at varying pH. stant, the influence of temperature on the dye adsorption by the com
posite under investigation could be well understood (Kurniawan et al.,
charged sites (-NH+ 3 ), thereby increasing the electrostatic attraction 2023b).
between the composite and the negatively charged Congo red dye The adsorption is endothermic if the dye removal rises with an
molecules. The protonation of functional groups at acidic pH enhanced increasing temperature. This could be due to enhanced dye molecule
the electrostatic interactions between the composite and the dye mole mobility and the rising amount of active adsorption sites. On the other
cules. This, in turn, led to increased adsorption capacity as more congo
red molecules were attracted to and adsorbed onto the positively
charged surface of the adsorbent (Batool et al., 2023b).
The adsorption of Congo red dye into the surface of the composite
was maximum within a certain pH range. This optimal pH range is
slightly acidic, where the protonation of functional groups is adequate to
facilitate strong electrostatic interactions without encountering exces
sive competition from other ions in the solution. This interaction was
prominent at acidic pH levels (Cheung et al., 2009). The
chitosan-grafted clay composite’s robustness was evident when exposed
to acidic environments, as suggested by the maximum dye adsorption at
pH 2. This indicates that the composite remained stable even under
highly acidic conditions and effectively removed Congo red dye mole
cules from the solution (Bellaj et al., 2024a; 2024b).
The resistance to acidity implies that the chemical structure and
integrity of the composite were maintained, enabling it to function
effectively as an adsorbent in acidic environments. Such resilience is
crucial for practical applications where solution pH might vary, ensuring
consistent and reliable composite performance for dye removal (Zhang
et al., 2018). As the solution pH became more alkaline, deprotonation of
the NH2- groups on the composite surface took place. Consequently, this
Fig. 10. Effects of temperature on dye adsorption by composite.
8
hand, if the dye adsorption diminishes with rising temperatures, the composite material, properties of dye adsorbate (such as concentration
adsorption reaction is exothermic. This study observed that the increase and molecular size), and environmental settings (such as pH). Exploring
in temperature enhanced the spontaneity and endothermicity of the the interactions between the composite and Congo red dye entailed
adsorption while promoting disorder at the composite’s interface. This understanding how the dye molecules were bound to the composite and
indicates that higher temperatures facilitated the dye removal on the how this interaction affected the adsorption of target dye. Investigation
composite surface, as this provided the required energy for the adsorp of the anionic dye’s adsorption pathway involved utilizing pseudo-first-
tion to occur and increased the mobility of the dye (Kurniawan et al., order (PFO), pseudo-second-order (PSO), and intraparticle diffusion
2023c). models.
Analysis of the kinetic models involved scrutinizing their rate con
3.2.6. Thermodynamic study stants and equilibrium capacities. Correlation coefficients were calcu
The elimination of Congo red dye by the adsorption onto the surface lated based on the experimental data (Table 4). This indicates the
of Clay-chitosan composites was also studied thermodynamically by goodness of fit between the experimental data and the predicted values
involving energetics and spontaneity data under the following experi from the kinetic models. The kinetic approach applied for modeling the
mental settings: 20 mg of dose, an initial dye concentration of 20 mg/L, pollutant removal by the dye is known as the pseudo-first-order
1 h of reaction time, and 600 rpm of agitation speed, while varying the adsorption principle. Based on this principle, the reaction rate at any
temperature from 298 to 328K and keeping other factors constant. given moment is directly proportional to the number of adsorption sites
To comprehend the adsorption’s nature, the thermodynamic pa on the surface of the adsorbent (Ho, 2004). Mathematically, the
rameters (ΔG◦ , ΔH◦ , ΔS◦ ) were evaluated. A negative ΔG◦ indicates pseudo-first-order equation is typically represented as Equation (5):
spontaneity, while ΔH◦ and ΔS◦ provide insights into the adsorption
k1
mechanism (physical or chemical adsorption). Mathematically, the log(qe − qt ) = log(qe ) − t (5)
2.303
thermodynamic parameters were determined based on Equations (3)
and (4): where: qe is the amount of dye absorbed at equilibrium (mg/g), qt is the
ΔGads = ΔHads – TΔSads (3) amount of dye absorbed at time t (mg/g), k1 is the first-order rate con
stant (L/min), and t is time (min). Hence, a linear trend is expected for
ΔG0 = − RT ln Kd (4) the plot of log (qe – qt) against t if the adsorption reaction follows the first
kinetics. The values of k1 and qe were determined from the slope and
where: T is temperature (K), R is universal gas constant (8.314 × 10− 3 intercept of the plot.
kJ mol− 1.K− 1), and Kc is distribution coefficient determined as follows: The pseudo-second-order kinetics also describes the dye adsorption
Kd = Qe/Ce; where Qe: is equilibrium adsorption capacity (mg/g), while onto adsorbents. In contrast to the pseudo-first-order model, this model
Ce is the equilibrium concentration of solute in solution (mg/L) assumes that the adsorption rate is contingent upon the surface area
Based on Table 3, the thermodynamic data for dye adsorption onto a occupied by the adsorbed molecules on the adsorbent (Ho and McKay,
composite surface can be interpreted as follows. 1999). The pseudo-second-order model is expressed as Equation (6):
t 1 1
a. Spontaneous adsorption: The negative values of the Gibbs free en = + t (6)
qt k2 q2e qe
ergy (ΔG◦ ) at all temperatures indicate that the adsorption was
spontaneous. This implies the dye molecules adsorbed onto the where: k2 is the pseudo-second-order rate constant (g/mg⋅min).
composite surface without requiring external energy input. The intraparticle diffusion kinetics of a pollutant on a composite is
b. Endothermic process: The positive enthalpy value (ΔH◦ ) of 8.82 kJ/ governed by the diffusion of the pollutant within the particles that
mol suggests that the adsorption process was endothermic. This in constitute the composite. Intraparticle diffusion involves the movement
dicates that heat was absorbed from the surrounding environment of the pollutant through the matrix of the composite in a progressive
during adsorption, increasing its thermal energy. manner over time. The intraparticle diffusion kinetics can be described
c. Increased disorder: The positive entropy value (ΔS◦ ) of 50.18 J/ mathematically as Equation (7):
mol⋅K indicates that the disorder at the composite interface increased
during dye adsorption. This suggests that the orientation of dye 12
qt = kp t +c (7)
/
molecules became more random or disordered upon adsorption onto

the adsorbent’s surface. where: qt and kp are the adsorption capacity at time t and intraparticle
diffusion rate constant, respectively.
Overall, dye adsorption onto the composite surface was spontaneous
and endothermic, accompanied by increased disorder at the interface of
the composite. This implies that the adsorption process naturally Table 4
occurred, absorbed heat from the surroundings, and resulted in a more Kinetic parameters of Congo red dye adsorption on composite at ambient
disordered arrangement of dye molecules on the composite’s surface. temperature.
Pseudo first order
3.2.7. Adsorption kinetics Ci (mg/L) 10 20 30 40
The study aimed to identify and comprehend the factors affecting the k1 (min− 1) 0.011 0.013 0.0062 0.00276
qe(exp) (mg/g) 190.36 39.28 49.19 55.25
speed of adsorption, which covered the properties of the clay-chitosan qe(cal) (mg/g) 19.35 40.45 54.26 54.84
R2 0.5664 0.6538 0.7692 08906
Table 3 Pseudo second order
3 3
k2 (g/mg.min) 6.016 × 10 − 24.97 × 28.28 × 38 × 10−
Thermodynamic parameters for Congo red dye adsorption by composite.
10− 3 10− 3
Temperature (K) Congo red dye qe(cal) (mg/g) 9.15 25.85 38.12 48.78
R2 0.9988 0.9979 0.9899 0.9992
Kd ΔG0 (KJ/mol) ΔH0 (KJ/mol) ΔS0 (KJ/mol)
Intraparticle Diffusion
298 11.65 − 6.08 +8.82 +50.18 kp (mg/(g.min(1/ 2.32 4.95 6.78 7.68
2)
308 13.67 − 6.69 )
318 15,51 − 7.24 C 4.41 6.36 3.74 5.3
328 16 − 7.55 R2 0.887 0.93 0.96 0.95
9
Table 4 demonstrates a high coefficient of regression (R2) for the nonlinearity: when n = 1, the adsorption is linear; when 0 < 1/n < 1, the
pseudo-second-order kinetics model, signifying a strong alignment with adsorption is considered favorable; and when 1/n > 1, the adsorption is
the experimental data. Coefficients of the intraparticle diffusion model deemed less favorable (Mahmoodi et al., 2011).
(kp, C), along with the R2 values, indicate the significance of intra The Temkin isotherm serves as a model to characterize the dye
particle diffusion as a controlling step in the dye adsorption by the adsorption onto an adsorbent surface based on physisorption. The model
composite. This finding offers a new understanding of the adsorption posits that the adsorption heat of all molecules within the layer di
process and associated kinetics, contributing to the comprehension and minishes linearly with coverage due to interactions between adsorbent
optimization of Congo red dye removal using the clay-chitosan and adsorbate (Ayawei et al., 2017). Mathematically, the Temkin
composite. isotherm is commonly formulated as Equation (11):
This suggests that the elimination of anionic dye by the adsorption
RT RT
process on the composite’s surface unfolds in two stages. Initially, the qe = Qm ln KT + Qm ln Ce (11)
ΔQ ΔQ
process commenced with the phenomenon of molecule diffusion of the
Congo red through pores in the composite matrix. This phase implies where: qe is the amount of adsorbate adsorbed per unit mass of adsor
that dye molecules permeated through the porous structure of the bent (mg/g), R is universal gas constant (8.314 J/(mol⋅K), T is the ab
composite, eventually accessing the functional groups of the composite. solute temperature (in Kelvin), KT is the equilibrium binding constant.
Subsequently, the process progressed with chemisorption on the specific Ce is the concentration of the solution, Qm is the maximum adsorption
sites of the adsorbent. This phase entails a stronger chemical interaction capacity (mg/g), and, ΔQ is the variation in adsorption energy.
between the Congo red dye and the reactive sites on the surface of the Adsorption isotherms elucidate the connection between the dye
composite, signifying a pronounced adsorption process. adsorbate (Congo red) and the adsorbent (clay-chitosan), unveiling in
sights into the interaction adsorption mechanism and the maximum
3.2.8. Adsorption isotherms adsorption capacity. Table 5 consolidates the constants associated with
Dye adsorption isotherms on the composite involved the application all of the isotherm models for dye removal. The regression coefficients of
of the Freundlich, Langmuir, and Temkin models. This linearization was dye removal suggest that the Langmuir isotherm well represented the
undertaken to verify the applicability of the models in which adsorption equilibrium data of the dye.
takes place, deducing the maximum adsorbed quantities and the affinity According to the Langmuir model, adsorption is assumed to take
of the target adsorbate with the adsorbent. place at specific homogeneous sites on the adsorbent surface, with
The Langmuir isotherm, established by Langmuir (1918), describes further adsorption ceasing once a site is occupied. The principal active
adsorption processes on surfaces, particularly those characterized by sites on the adsorbent surface, specifically the –NH2 and –OH groups,
homogeneous surfaces forming monolayers (Langmuir, 1918). Never facilitate the adsorption of Congo red dye as a monolayer on the sites.
theless, the Langmuir model relies on several assumptions and may not The Langmuir isotherms yield a maximum adsorption capacity of 84.74
fully capture the complexity of adsorption behavior in intricate systems. mg/g for Congo red dye. A comprehensive understanding of the
The Langmuir isotherm is commonly expressed mathematically as isotherm models and their parameters assists in optimizing the adsorp
Equation (8): tion process under varying temperatures.
Ce 1 Ce
= + (8)
qe KL Qm Qm 4. Theoretical study
where: qe (mg/g) is the adsorbed amount of the dye during adsorption 4.1. Quantum chemical calculations of chitosan
equilibrium, Ce is the adsorbate equilibrium concentration (mg/L), and
KL. is the Langmuir equilibrium constant (L/mg), and Qm is the 4.1.1. Theoretical parameters
maximum adsorption capacity (mg/g). The essential characteristic of The scratching of the chitosan monomer on the surface of raw clay
the Langmuir isotherm can be presented by the dimensionless constant was investigated using a density functional theory (DFT) method. The
(RL) defined by (Equation (9): study aimed to enhance the understanding of the compound’s molecular
1 structure in its ground state. Computational calculations were carried
RL = (9) out using the Gaussian 03 package and the Gaussian View molecular
1 + KL C0
visualization method.
where: C0 is initial dye concentration (mg/L). RL values indicate the type The analysis involved a HOMO-LUMO analysis, which tested both
of isotherm: irreversible (RL = 0), favorable (0 < RL < 1), and unfa the highest occupied molecular orbital (HOMO) and the lowest unoc
vorable (RL > 1) (Mahmoodi et al., 2006). cupied molecular orbital (LUMO) of chitosan. Various quantum
The Freundlich isotherm is also employed to describe adsorption
where the adsorbent surface is heterogeneous, and the dye removal Table 5
mechanism involves multilayer adsorption. Nevertheless, this model is Isotherms parameters of dye adsorption onto composite.
empirical and does not offer mechanistic insights into adsorption Temperature 298 K 308K 318K 328 K
(Freundlich, 1906). The Freundlich isotherm can be expressed as
Langmuir isotherm
Equation (10): KL 0.365 0.318 0.181 0.413
Qm 77.5 80 82 84.74
1
log qe = log KF + log Ce (10) RL 0.12 0.14 0.2 0.1
n R2 0.9971 0.9832 0.9249 0.9998
Freundlich isotherm
where: qe is the amount of solute adsorbed per unit mass of adsorbent KF 15.93 20.97 25.38 3.79
(mg/g), KF is the Freundlich constant, Ce is the equilibrium solute con 1/n 0.536 0.4747 0.4272 0.94
centration in the solution, and 1/n is the Freundlich exponent, which R2 0.806 0.872 0.967 0.936
Temkin isotherm
indicates the favorability of adsorption and typically ranges between
Qm 77.5 80 84.74 82
0 and 1. ΔQ 128.52 157.62 155.5 162
According to the Freundlich isotherm, the quantity of solute adsor ln KT 0.43 1.02 1.4 1.55
bed exhibits a nonlinear increase as the equilibrium concentration in KT 1.53 3.18 4.05 4.71
creases. The exponent 1/n within Equation (10) signifies the degree of R2 0.8999 0.8885 0.9985 0.9657
10
chemical parameters were computed, including electronic energy, reveals an obvious interplay of electrophilic and nucleophilic behavior,
EHOMO, ELUMO, molecular dipole moment (μ), chemical hardness (η), particularly at oxygen (O) and hydrogen (H) atoms, as they interact with
softness (S), and electrophilicity index (N) (Table 6). the surface of the adsorbent. This behavior was due to the distribution of
Table 6 presents the quantum chemical parameters of chitosan nucleophilic and electrophilic sites around their atoms. Notably,
monomer, offering insights into its molecular properties. The energy gap nucleophilic attacks were identified at atoms H19, H11, and C1,
between EHOMO and ELUMO (ΔE) was highlighted as a significant factor exhibiting high P.K.- values, reaching up to 0.300. Conversely, atoms like
influencing the reactivity and chemical stability of the molecule. Chi O16 were recognized as electrophilic attacks with elevated P+ k values,
tosan demonstrated a substantial energy gap, suggesting a relatively facilitating electrostatic attraction between the chitosan molecule and
lower stability and reactivity. Additionally, this polymer exhibits a high the positive charge on the clay’s surface. The insights shed light on the
EHOMO value, indicating its tendency to donate electrons to empty or specific sites of reactivity within chitosan, implying its interactions with
bitals with reduced energy, thereby facilitating greater intramolecular other substances during adsorption.
charge transfer to the clay’s surface.
Molecular electrostatic potential (MEP) mapping was utilized to 4.2. Quantum chemical calculations of dye
investigate atomic and molecular properties, as well as the overall
electrostatic effects resulting from the total charge distribution of the 4.2.1. Global theoretical parameters
molecule in space. Fig. 11 displays the energy gap between HOMO- The DFT method used the B3LYP/DGDZVP level in the Gaussian 09
LUMO and the MEP of chitosan. MEP mapping employs distinct colors program to calculate quantum chemical reactivity parameters and the
to highlight the electrostatic characteristics of chitosan, with red rep ESP of the dye. Optimized structures were used to determine the reac
resenting the most electrophilic sites and blue indicating the most tivity parameters. Theoretical reactivity parameters derived from DFT
nucleophilic regions. have been studied to characterize the reactivity of organic molecules.
In the Molecular Electrostatic Potential (MEP) analysis of neutral In this study, the theoretical parameters were utilized to elucidate
chitosan, negative charges were observed surrounding the oxygen het the interactions between the dye and the surface of the adsorbent. To
eroatoms. The O atoms were prone to electrophilic attacks due to the assess the dye’s reactivity, EHOMO (Energy of the Highest Occupied
characteristics. Conversely, C atoms were uniformly depicted in green, Molecular Orbital), ELUMO (Energy of the Lowest Unoccupied Molecular
implying a neutral charge throughout the molecule. Additionally, Orbital), chemical hardness (η), softness (S), electronic chemical po
electron-deficient regions were indicated by the H atoms associated with tential (μ), nucleophilicity (N), and electrophilicity (ω) were calculated
the –NH2 and –OH groups, implying nucleophilic interaction sites within using the DFT. They provide an understanding of the electronic structure
the chitosan molecule. This explains the specific areas of chitosan where and reactivity of the Congo red dye, promoting a better knowledge of its
interactions with other molecules might occur, whether via electrophilic interactions with the surface of the composite (Sarode et al., 2019).
or nucleophilic mechanisms. Nevertheless, theoretical investigations Table 7 presents parameters that offer an understanding of the
rely on assumptions that do not fully capture the complexities of the reactivity, electronic structure, and stability of the dye molecule, which
adsorption. Incorporating realistic models and experimental validation are crucial for understanding its behavior in various applications such as
could enhance the reliability of theoretical predictions. dyeing. A stronger attraction between molecules was signified by a
larger dipole moment, as exemplified by the dye with a dipole moment
4.1.2. Local theoretical parameters of chitosan of μ = 4.8174 Debye. Conversely, the electrophilicity index (ω =
The local electrophilicity (ωk) and local nucleophilicity (Nk) of chi 43.1010 eV) was notably high, indicating the dye’s electrophilic nature.
tosan were determined using Parr functions P+ k and Pk , respectively,
−
Fig. 13 illustrates the optimized geometric structure alongside the
derived from Mulliken analysis of atomic spin density (ASD). Both most and least occupied molecular orbitals, as well as the density of state
Equations (12) and (13) were employed to compute ωk and Nk. The diagrams. The electron density distribution reveals that the HOMO
resulting P+k , Pk , ωk, and Nk values were then calculated and depicted in
−
density region extended across the sulfonate (SO−3 ) and carbon (C) atoms
Fig. 12 for presentation and analysis. Valuable insights into the localized within the dye’s electrical characteristics. In contrast, the LUMO areas,
electrophilic and nucleophilic properties of chitosan are provided by this characterized by high electron density, were saturated with approxi
approach, aiding in the understanding of its reactivity and potential mately half of the SO−3 on both ends of the molecule. This suggests that
interactions in diverse environments. the aromatic ring and the oxygen (O), sulfur (S), and nitrogen (N) het
eroatoms served as adsorption centers due to electron delocalization
ωK = ω.P+
k (12)
around the regions, likely functioning as subtle adsorption sites. The
NK]N. P.K.- (13) difference in energy between the HOMO-LUMO orbitals warrants
consideration, as a low gap energy was observed.
The k,
P+ P−k ,
ωk, and Nk values were calculated and presented in
Fig. 12. 4.2.2. Molecular electrostatic potential (MEP) of Congo red dye
The distribution of Parr functions, electrophilicity (ωK), and nucle MEPs analysis primarily focuses on electron density distribution
ophilicity (N.K.) across chitosan is illustrated in Fig. 12. The analysis across a molecule’s surface. This analysis served as a valuable tool for
elucidating electrophilic and nucleophilic attack reactions, H-bonding,
Table 6 and relative polarity. The colors displayed in MEPs indicate the
Theoretical chemical parameters of chitosan monomer. magnitude of the electrostatic potential with decreasing strength in
Molecular properties Values (eV) order: red (indicating a strong negative electrostatic potential, favoring
electrophilic attacks), yellow (representing a moderately negative po
Electronic energy − 15928.95
EHOMO − 10.2575
tential), blue (reflecting a strongly positive potential, associated with
ELUMO 6.0207 nucleophilic tendencies), and green (implying a light potential)
E
μ = HOMO
+ ELUMO − 2.1184 (Fig. 14).
2 In the representation of MEP (Molecular Electrostatic Potential),
η = EL-EH 16.2782
μ2 0.1239 nucleophilic sites were found to be concentrated around the sulfonate
ω =
2η groups, rendering them susceptible to electrophilic attacks. The visual
S =
1 0.0614 ization’s transition from dark blue to dark red indicates a movement of
η electron-rich areas toward regions deficient in electrons. Moreover, a
N ¼ EHOMO – EHOMO(TCE) 0.8889
consistent green color envelops all carbon atoms within the benzene
11
Fig. 11. Depiction of the energy HOMO-LUMO and MEP of chitosan.
Fig. 12. Distribution of Parr functions, electrophilicity (ωK), and nucleophilicity (N.K.) for chitosan.
involves key steps, as elucidated by various analytical techniques and

Table 7
theoretical calculations. Initially, changes in diffraction peaks following
Theoretical parameters of dye.
the adsorption process were studied through X-ray diffraction (XRD)
Molecular properties (B3LYP/DGDZVP) Values (eV) analysis. Shifts towards lower angles were observed, potentially indi
Electronic Energy − 76429.76 cating an interaction between the composite and Congo red dye.
EHOMO − 6.2033 Notably, a reduction in peak width was evident, implying crystalline
ELUMO 5.7864
−
disorganization associated with the dye interaction.
E + ELUMO 5.9948
μ = HOMO
−
2 Furthermore, Fourier-transform infrared spectroscopy (FT-IR) anal
η = EL-EH 0.4169 ysis of the composite surface, before and after dye adsorption, indicates
μ2 43.1010 a slight decrease in peak absorption intensity and a shift in functional
ω =
2η
groups such as –NH2 and –OH. The groups served as active sites on the
1 2.3986
S =
η adsorbent’s surface during adsorption. Additionally, energy-dispersive
N ¼ EHOMO – EHOMO(TCE) 3.1653 X-ray analysis reveals the existence of S atoms on the composite sur
face after adsorption, suggesting an interaction between the sulfonic
functional group (SO−3 ) of the CR and the composite surface.
cycles, indicating an evenly distributed electron density. In contrast, the Density functional theory (DFT) calculations highlight the impor
N atoms exhibit blue colors, suggesting their high positive charges. The tance of –NH2 and –OH groups on the composite’s surface in facilitating
blue-colored areas denote electron-deficient zones, creating potential dye adsorption. The adsorption mechanism relies on the interaction
sites for interactions with the nucleophiles. between the composite and the SO−3 functional group of the dye. H-
bonds between –NH2 and –OH groups on the composite’s surface and the
5. Adsorption mechanism of Congo red dye dye’s SO−3 group contributed to this adsorption.
Moreover, pH plays a role in determining the dye removal by the
The underlying mechanism of the adsorption for Congo red removal composite. Optimal adsorption of the anionic dye occurred at acidic pH
12
Fig. 13. Density of state (DOS) spectrum and surface HOMO-LUMO of dye.
due to electrostatic attractions between dye molecules and the surface of

chitosan-grafted clay. Protonation of chitosan’s –NH2 groups under
acidic conditions resulted in the formation of –NH+ 3 groups, which
attracted the dye’s negatively charged SO−3 groups. This explained the
increased dye adsorption at acidic pH, with the highest dye removal at
pH 2 (Juang and Shao, 2002).
The robustness of the chitosan-grafted clay composite was evidenced
by its stability and effectiveness in acidic environments, suggesting that
its chemical structure and integrity remain intact at acidic conditions.
This resilience ensures consistent and reliable performance of the com
posite material for dye removal, even in challenging acidic environ
ments. Furthermore, an increase in the efficiency of Congo red dye
elimination was observed when the solution pH was lower than the zero-
point charge (pHzpc) of the adsorbent, indicating the importance of
electrostatic interactions in the adsorption. Overall, the adsorption
mechanism of Congo red dye on the surface of the composite involves
Fig. 14. MEP surface and contour image of Congo red dye molecules. interactions between functional groups, electrostatic attractions, and
pH-dependent phenomena (Fig. 15) (Bellaj et al., 2024b).
Fig. 15. Mechanism of dye adsorption into the surface of the composite.
13
6. Comparation of adsorption capacity between clay-chitosan Table 8

composite and other adsorbents Comparison of adsorption capacities of various composites for Congo red dye
removal.
The comparative evaluation of this composite for eliminating the Type of adsorbent Qmax (mg/g) Reference
synthetic dye from wastewater with a particular focus on Congo red dye Na-bentonite 35.84 Vimonses et al. (2009)
is presented in Table 8. Maximum adsorption capacities of various ad Australian kaolin 5.44 Vimonses et al. (2009)
sorbents, including natural clay, bentonite, kaolin, montmorillonite, Montmorillonite 2.09 Karthikaikumar et al. (2014)
chitosan hydrobeads, chitosan-montmorillonite composite, and the clay- Chitosan hydrobeads 93.4 Chatterjee et al. (2007)
Chitosan-clay composite 84.74 Present study
chitosan composite used in this study, are presented for comparison and
evaluation.
Table 8 explains that the clay-chitosan composite exhibits a notable comprising natural clays and chitosan waste, has emerged as a novel and
maximum adsorption capacity of 84.74 mg/g for Congo red. This places effective adsorbent for treating wastewater containing refractory dyes.
it among the top-performing adsorbents in the comparison. The high
adsorption capacity of the composite was due to the synergistic effect CRediT authorship contribution statement
between the clay surface and the active sites of chitosan, which created
additional functional groups for adsorption. While higher adsorption Mouhsine Bellaj: Conceptualization. Aicha Naboulsi: Formal
capacities might be demonstrated by certain adsorbents, as compared to analysis, Data curation. Khalid Aziz: Project administration, Funding
the composite, the latter was promising for being environmentally acquisition. Abdelmajid Regti: Resources, Project administration.
friendly and low cost (Sniatala et al., 2022). Mamoune El Himri: Methodology. Mohammadine El Haddad: Vali
Nevertheless, batch tests did not fully replicate real-world conditions dation. Mounir El Achaby: Software. Abdelkrim Abourriche: Visual
where water treatment occurs continuously. Real-world water sources ization. Lhoucine Gebrati: Project administration. Tonni Agustiono
contain multiple contaminants, and the performance of the composite Kurniawan: Writing – review & editing. Faissal Aziz: Writing – review
material in removing other pollutants may differ. Batch tests might not & editing, Writing – original draft, Supervision.
provide sufficient insight into the sorption kinetics of the composite
material. Understanding how quickly the material reaches equilibrium Declaration of competing interest
with the dye solution is crucial for process optimization and practical
application. Therefore, the effectiveness observed in batch tests is not The authors declare that they have no known competing financial
directly translated to practical applications (Ulfat et al., 2023). interests or personal relationships that could have appeared to influence
Combining chitosan and clay can be challenging due to their oppo the work reported in this paper.
site hydrophilic and hydrophobic properties (Lo et al., 2009). However,
chitosan derivatives can help minimize this barrier and enhance Data availability
compatibility between the two materials, thereby stabilizing the com
posites even under extreme operating conditions. Scaling up these Data will be made available on request.
findings to industrial or municipal levels might present challenges in
terms of maintaining performance, cost-effectiveness, and practicality. References
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Contents lists available at ScienceDirect

2. Materials and methods

Chemicals and reagents were analytical grades and utilized as

2.2. Methods analyzed using a combination of scanning electron microscopy (MEB)

Congo red (CR) Azo 22120 696,665 g/mol Neutral 498

Fig. 8. Particle size affects dye removal

diminished the electrostatic attraction between the composite and dye

3.2.5. Effects of temperature on dye removal

molecules became more random or disordered upon adsorption onto

Fig. 11. Depiction of the energy HOMO-LUMO and MEP of chitosan.

involves key steps, as elucidated by various analytical techniques and

due to electrostatic attractions between dye molecules and the surface of

6. Comparation of adsorption capacity between clay-chitosan Table 8

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