Adsorption (2024) 30:1643–1661

https://doi.org/10.1007/s10450-024-00527-x

Fabrication of nanozeolite-Y/chitosan composite based on rice

husks for efficient adsorption of methylene blue dye: kinetic and
thermodynamic studies
Amany G. Braish1 · Asaad F. Hassan1 · Shimaa A. El-Essawy1 · Mohsen M.T. El-Tahawy1

Received: 7 June 2024 / Revised: 26 July 2024 / Accepted: 7 August 2024 / Published online: 2 September 2024
© The Author(s) 2024

Abstract
In this work, three solid adsorbents were synthesized, namely, nanozeolite-Y prepared from rice husks ash by a sol-gel
method as a green biosource (ZN), chitosan as a cationic biopolymer (CS), and nanozeolite-Y/chitosan composite (CSZ).
An eco-friendly composite that consists of chitosan and nanozeolite-Y was used to combine the advantages of nanoparti-
cles with biopolymers two materials to increase the removal % of methylene blue dye. All the synthetized solid adsorbents
were investigated using TGA, nitrogen adsorption, SEM, TEM, FTIR, XRD, and zeta potential. The results showed that
CSZ particles had a high specific surface area (432.3 m2/g), mesoporosity (with an average pore diameter of 2.59 nm),
a smaller TEM particle size (between 28.6 and 60.7 nm), a lot of chemical functional groups, and high thermal stabil-
ity. CSZ exhibited the maximum adsorption capacity (141.04 mg/g) towards methylene blue. The adsorption nature of
methylene blue onto CS and CSZ is endothermic, spontaneous, and a physical adsorption process, while it is exothermic,
nonspontaneous, physical adsorption process in the case of ZN, as confirmed by thermodynamic results. Pseudo-second
order, Elovich, Dubinin-Radushkevich, Freundlich, Langmuir, Temkin, and adsorption models all fit the MB adsorption
well, with correlation coefficients reaching about 0.9997. Nitric acid was found to be the best desorbing agent, with a
desorption efficiency of about 99%.

Keywords Nanozeolite-Y · Chitosan · Rice husks · Methylene blue · Adsorption

1 Introduction humans and animals (Abdulridha, Jiao et al. [1], Rehan,

Rasee et al. [51]). The presence of pigments in the body can
Wastewater discharge without sufficient treatment causes have extremely harmful effects on humans who consume
substantial environmental hazards. Water pollution affects large amounts of water. These effects include gastrointesti-
the health of billions of people, inhibits global economic nal distress, vomiting, chest pain, diarrhea, dyspnea, exces-
progress, and has an adverse effect on climate change. sive sweating, intense headaches, and cyanosis, in addition
Due to industrial activity, population growth, and human to skin irritation and itching (El Nemr, Shoaib et al. [18]).
behavior, environmental contamination has significantly Methylene blue (MB) [3, 7-bis (dimethyl amino) phenothi-
increased (El Nemr, Shoaib et al. [18], Najafi, Abednatanzi azine chloride tetra methylthionine chloride] is one of the
et al. [45]). The industry of dyes releases a lot of wastes synthetic dyes used as a coloring agent for papers, wool,
into the environment, which has the potential to poison both silk, and cotton. Due to the unique stability of the aromatic
ring in the MB molecular structure, the substance is both
carcinogenic and non-biodegradable. The health hazards
related to MB include genitourinary, respiratory, cardiovas-
Asaad F. Hassan
asmz68@sci.damu.edu.eg cular, central nervous system disorders, and dermatological
impacts (Oladoye, Ajiboye et al. [46]). As a result, before
Mohsen M.T. El-Tahawy
mohsen.eltahawy@sci.dmu.edu.eg the effluent is dominated in the water system, the dyes must
be removed from it to the necessary levels.
1
Chemistry Department, Faculty of Science, Damanhour
University, Damanhour, Egypt

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1644 Adsorption (2024) 30:1643–1661

Advanced wastewater treatment techniques frequently Marinov et al. [10]), and bamboo leaf (Ahmad, Daou et al.
involve chemical advanced reduction processes and photo- [2]) are all biomass sources of silica for zeolite synthesis.
catalysis (Zhou, Yu et al. [64]), physical procedures such as The main components of the by-product from a rice mill are
membrane filtration (Zhou, Xiao et al. [65] and ion exchange rice straw, rice plant materials, rice husks, etc. Rice husks
(Lahiri, Zhang et al. [40]), biological as microbial degra- ash is composed of 4–12% carbon, 85–95% silica (Si), and
dation (Tomar, Kahandawala et al. [61]), physicochemical other residues of metal oxides. Rice husks (RH) have high
ozonation (Oladoye, Ajiboye et al. [47]), electrochemical surface area and a porous, crystalline structure that ranges
oxidation, advanced oxidation processes (Hama Aziz, Mus- from 70 to 100 m2/g, bulk density of 0.25 to 0.30 g/cm3, and
tafa et al. [23]), and adsorption processes (Zhou, Yu et al. it can hold twice as much water as it weighs. All of these
[64]). Adsorption is regarded as one of the most appealing characteristics make the RH a low-cost, high-efficiency filter
and adaptable treatment approaches due to its simplicity, (Pillai, Dharaskar and Pandian [50]). Making an adsorbent
great efficacy, cheap cost, and low energy usage. Activated with a high adsorption capacity, performance, selectivity,
carbons (Kumar, Pandey et al. [39]), zeolites, alumina, quick adsorption kinetics, and reusability is a challenge in
silica gel (Gupta, Prajapati et al. [21]), natural materials the adsorption process [52].
as wood, coal, chitin/chitosan, and clay (Ahmed, Hameed Chitosan (CS) is a cationic biopolymer made up of D-glu-
and Hummadi [4]), and nanomaterials have all been con- cosamine units and is prepared by the alkaline N-deacety-
sidered as dye removal adsorbents. However, some of lation of chitin. Chitin is found in the shells of crustaceans,
them have problems such as difficulty in big consumption, insects, and other organisms. Some of the great chemical
regeneration, and limited effective life, necessitating the and biological properties of CS are that it is biocompatible,
development of novel adsorbents with high practicability. has high chemical reactivity, is non-toxic, biodegradable,
Because of the unique qualities of nanomaterials, such as hydrophilic, has the ability to adsorb, chelate, be chiral,
a higher number of active sites and a larger surface area, and be antibacterial. The hydroxyl (-OH) and amino (-NH2)
nanomaterials have recently received increased interest in groups in the CS chain serve as possible adsorption sites for
the removal of organic dyes. They can be changed with a a variety of water contaminants, including medicines, dyes,
variety of chemical groups to improve their chemical affin- and metal ions. The physicochemical characteristics of CS
ity for target chemicals. Many nanomaterials, including sili- have been described via a variety of techniques, including
con nanoparticles, carbon nanotubes, nanoclay, nanofibers, crosslinking, grafting, and compositing. The crosslinking
polymer-based nanomaterials, and aerogels, have been used reaction is the most efficient strategy of these techniques for
in adsorption (Hassan, El-Naggar et al. [27]). The removal enhancing the mechanical and chemical stability of CS. For
of synthetic organic dyes from water and wastewater has the removal of dyes from aqueous solutions, cross-linked
been effectively carried out by natural nanomaterials, such CS adsorbents are frequently used. Zeolite has the nega-
as nanozeolites, because of their intrinsic qualities (ion tive charge of oxygen connected to aluminum atoms in the
exchange capacity, high chemical stability, meso and micro- framework, which may be connected with chitosan. Zeolite/
porosity, high surface area, and unique electronic behavior) chitosan composites are getting more focus in the field of
and size-dependency (Oviedo, Oviedo et al. [49]. pollutants removal from wastewater, such as the adsorption
Zeolite nanoparticles (ZN) are crystalline compounds of methyl orange, Fe3+, Ni2+, and Cr6+ ions, and humic acid.
made up of AlO4 and SiO4 that have been connected to an Chitosan-epichlorohydrin/zeolite composite (CHS-ECH/
ordered system to produce a consistent crystal structure. ZL) is an example of a composite that is used to extract
Two faujasite (FAU) varieties of zeolites that are of particu- MB dye from aqueous environments. For MB and reactive
lar interest are zeolite-X and zeolite-Y. The ratio of silica red 120 (RR120) at 30 °C, the measured adsorption capaci-
to alumina, which is 2:4 for zeolite-X and more than 3 for ties of CHS-ECH/ZL are 156.1 and 284.2 mg/g, respec-
zeolite-Y, serves as a means of identification (Hassan, Alafid tively [37]. A magnetic sodium alginate-modified zeolite
and Hrdina [25]). Specifically, the faujasite (FAU) Y zeolite (SA/zeolite/Fe3O4) composite with an adsorption capacity
is considered one of the most widely used zeolites because of 181.9 mg/g is another example of removing MB from
it has a spherical super cage with a diameter of 1.3 nm and wastewater (Liu, Li and Zhou [42]).
a three-dimensional pore structure with a window aperture This work aims to discuss the preparation of nanozeo-
of around 0.74 nm (Abdulridha, Jiao et al. [1]). Nanosilica lite-Y (ZN) using silica nanoparticles extracted from rice
is utilized to adsorb dyes because it is non-toxic, chemically husks (RH) by sol-gel method and its modification with chi-
stable, has large specific surface area, and is spherical, all tosan (CS) for synthesizing nanozeolite composite (CSZ).
of which provide more adsorption sites for organic mole- The synthesized adsorbents were investigated by different
cules (Du, Zhang et al. [15]). Bagasse ash (Oliveira, Cunha physicochemical tools such as XRD, TGA, TEM, SEM,
and Ruotolo [48]), rice husks ash, coal fly ash (Boycheva, FTIR, zeta potential, and N2 adsorption/desorption. Batch

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Adsorption (2024) 30:1643–1661 1645

adsorption of methylene blue was studied under various Bortolatto, Boca Santa et al. [9], Hassan, Alafid and Hrdina
adsorption conditions, considering the effects of dosage, [25]). Sodium silicate (Na2SiO3) was prepared from SN
pH, temperature, initial concentration, and shaking time of nanoparticles by dissolving SN in 2.5 M NaOH under
the adsorbate. Both thermodynamics and kinetics parame- heating and continuous stirring. Two Teflon beakers were
ters were investigated to identify the mechanism and nature prepared: the first one contained 10 mL of 5.09 M sodium
of methylene blue adsorption. hydroxide and 2.09 g of sodium aluminate, while the sec-
ond one contained 10 mL of 5.09 M sodium hydroxide and
22.72 g of sodium silicate. The two solutions were stirred
2 Materials and methods and allowed to develop for 20 h until they became homoge-
nous. The silicate solution was combined with the aluminate
2.1 Materials solution and stirred for 6 h until a solidified gel product was
formed. The gel was heated, cooled, then rinsed with water
Rice husks were gathered from a local rice mill (Dam- till pH 9, centrifuged, and dried overnight at 70 °C. Finally,
anhour, Egypt). Sodium aluminate was purchased from zeolite-Y nanoparticles were produced and stored in clean,
Sigma-Aldrich Co., Ltd., USA. Sodium hydroxide and dry bottles.
hydrochloric acid were obtained from El-Nasr for the chem-
ical and pharmaceutical industry Co., Egypt. Chitosan was 2.2.3 Preparation of chitosan beads (CS)
purchased from Alfa-Aesar Co., Germany. Methylene blue
(MB) and acetic acid were obtained from Piochem Co., Chitosan insoluble beads were produced by dissolving 2.0 g
Egypt. All chemicals were used without further treatment. of solid chitosan in 150 mL of 2% aqueous acetic acid for
2 h under continuous stirring. The final solution was dropped
2.2 Solid adsorbents preparation with a fine syringe into a 2 M NaOH solution, and the result-
ing precipitate was filtered and washed several times with
2.2.1 Preparation of nanosilica from rice husks (SN) distilled water before drying at 70 °C for 24 h (CS) [30].

Rice husks (RH) were ignited at 800 °C to a constant weight, 2.2.4 Preparation of nanozeolite-Y/chitosan composites
and the disappearance of the gray color indicated the pro- (CSZ)
duction of rice husks ash (RHA). RHA (20 g) was refluxed
with 30 mL of 2.0 M HCl for 4.0 h at 120 °C under magnetic Nanozeolite-Y/chitosan composite was produced by dis-
stirring. The separated solid residue was washed numerous solving 2 g of chitosan in 150 mL of 2% aqueous acetic acid
times with distilled water followed by drying at 110 °C. For for 2 h while stirring. A certain weight of the produced nano-
five hours, the previously dried solid residue was refluxed in zeolite-Y was separately suspended in 25 mL of distilled
2.5 M NaOH with constant magnetic stirring. The obtained water using a sonication technique and then transferred to
colorless viscous residue (sodium metasilicate, Eq. 1) was a chitosan solution. The previous mixture was stirred con-
allowed to cool down. In a Teflon beaker, 5.0 M HCl was stantly for 6 h to ensure homogenous mixing and dropped
added drop by drop to the previous viscous solution until the into a 200 mL, 2 M solution of NaOH. After filtering and
pH reached 2, followed by the dropwise addition of NH4OH washing with distilled water, the solid composite was left to
till pH 8.7, and nanosilica particles were formed according dry overnight at 70 °C (CSZ).
to Eq. 2. Then, the nanosilica particles were cleansed using
hot distilled water and subsequently dried at a temperature 2.3 Characterization of the prepared solid
of 120 °C (SN) (Hassan, Alafid and Hrdina [25]): adsorbents

SiO2 (RHA) + 2NaOH → Na2SiO3 + H2 O (1) Thermal, textural, and chemical characterization methods
are important for evaluating the characteristics of solid
2HCl + Na2SiO3 → SiO2 (SN) + 2NaCl + H2  (2) adsorbent.
Thermogravimetric analysis (TGA) was performed for
RH, SN, ZN, CS, and CSZ to determine the thermal behav-
2.2.2 Preparation of nanozeolite-Y (ZN) ior of the samples that were produced using a thermal ana-
lyzer apparatus (SDT Q600 V20.9 Build 20) up to 800 °C.
Zeolite-Y nanoparticles were fabricated based on meth- All samples (SN, ZN, CS, and CSZ) were determined
ods described by Bortolatto et al. and Rahman et al. with for SBET (specific surface area, m2/g), VT (total pore volume,
slight modifications (Wan Nik, Hasnida and Rahman [63], cm3/g), and r̅ (average pore diameter, nm) utilizing nitrogen

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1646 Adsorption (2024) 30:1643–1661

adsorption at − 196 °C using a NOVA2000 gas sorption where Co and Ce are the starting and equilibrium concentra-
analyzer (Quantachrome Corporation, USA). tions of the dye (mg/L), respectively, W is the mass of solid
X-ray diffraction analysis (XRD) for SN, ZN, CS, and adsorbent (g), and V (L) is the solution volume of MB.
CSZ was performed using a D8 Advance diffractometer Different adsorption conditions were employed to study
for studying the crystal structures and particle size of solid the adsorbent dosage (0.2–2.4 g/L), pH (2 − 12), contact
adsorbents. X-ray examinations were performed by using a time (0.25–25.0 h), initial adsorbate concentration (25–
thin powder sample deposited onto an oriented monocrys- 700 mg/L) according to the adsorbent adsorption capacity,
talline quartz plate for exposure to a Cu Kα X-ray source and applied adsorption temperature effect (20, 30, 40, and
(λ = 1.5406 Å). The source of radiation operates at a cur- 47 °C). The removal percent (R%) of MB dye was calcu-
rent of 40 mA and 40 kV with nickel-filtered radiation. The lated using Eq. 4.
solid samples were evaluated at room temperature over the
2θ range of 10°–50°. C0 − Ce
Removal percent (R%) = × 100 (4)
The fabricated solid materials (SN, ZN, CS, and CSZ) C0
were investigated using a Fourier transform infrared spec-
trometer (FTIR) between 400 and 3800 cm− 1 range utiliz-
ing Mattson 5000 FTIR spectroscopy. Zeta potentials for all 2.5 Models of adsorption isotherm
adsorbents were determined by Zetasizer Nano S, Malvern
Instruments, UK. To study the availability of MB adsorption on the surface
Scanning electron microscopy (SEM) was used to deter- of solid adsorbents, a variety of isotherms have been used
mine the morphological structure of (SN, ZN, CS, and CSZ) in adsorption systems, such as the Langmuir, Freundlich,
as solid adsorbents using a JEOL-JSM-7500 F instrument. Temkin, and Dubinin-Radushkevich models.
The samples’ surfaces were vacuum evaporated to apply a
thin layer of gold (3.5 nm) to reduce the impact of the elec- 2.5.1 Langmuir adsorption model
tron beam on sample charging.
Transmission electron microscope (TEM) was examined The Langmuir model is applied to the monolayer adsorption
for SN, ZN, CS, and CSZ as solid adsorbents through a of adsorbate onto a finite number of equivalent localized
JEOL-JEM-2100 (Tokyo, Japan). The samples were dried sites of homogenous surface of adsorbent with no interac-
in an oven at 110 °C and dispersed in an anhydrous etha- tion between adsorbates and can be represented by Eq. 5.
nol solution under ultrasonication for 15 min before being
placed on Cu grid and coated with lacey carbon film. Ce 1 Ce
= + (5)
qe KLqm qm
2.4 Batch adsorption of methylene blue (MB)
where the maximum adsorption capacity (qm) and equilib-
Batch experiments for the adsorption of MB onto the sur- rium adsorption capacity (qe) are, respectively, expressed in
faces of ZN, CS, and CSZ were performed through various mg/g. The Langmuir adsorption constant is KL (L/mg).
application conditions to determine the maximum adsorp- The dimensionless separation factor (RL) was calculated
tion capacities, the optimum adsorption conditions, thermo- to give information on the feasibility of MB adsorption.
dynamic parameters, and kinetic parameters.
Adsorption of MB from aqueous solution at the surface 1
RL = (6)
of samples was investigated by mixing 50 mL of MB solu- 1 + KLC0
tion with a known mass of adsorbents (0.1 g) at pH 6.5 for
30 h as a shaking time at 20 °C. The solution was filtered Herine, RL value shows the nature of adsorption to be favor-
with Whatman filter paper grade 1, where the first five milli- able in the case of 0 < RL < 1, unfavorable when RL is greater
liters of filtrate were rejected, and the residual concentration than 1, linear if RL = 1, and irreversible in the case of RL = 0.
of methylene blue was determined by a UV-vis spectropho-
tometer (λmax = 662 nm). 2.5.2 Freundlich adsorption model
The capacity of adsorption qe (mg/g) at equilibrium was
calculated using the following equation: This model illustrates the reversible nature of the adsorption
technique and describes monolayer and multilayer adsorp-
qe =
(C0 − Ce ) × V
(3) tion on heterogeneous solid surfaces:
W

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Adsorption (2024) 30:1643–1661 1647

1
Ln qe = Ln K F + Ln C e (7) pseudo-first order (PFO, Eq. 13), pseudo-second order
n (PSO, Eq. 15), and Elovich (Eq. 16):

where KF and n denote constants associated with the adsorp- Ln (qe − qt ) = Ln qe − k1t (13)
tion intensity and capacity, respectively (Shaltout, El-Nag-
gar et al. [55]). qt =
(C0 − Ct )
× V (14)
W
2.5.3 Temkin adsorption model
t 1 1
= + t (15)
The Temkin model (Eq. 8) shows the effect of indirect qt K2 qe2 qe
adsorbate–adsorbent interactions; the heat of adsorption
decreases linearly rather than logarithmically with surface 1 1
qt = Ln α β + Ln t (16)
coverage, and is expressed by: β β

qe = β Ln K T + β Ln C e (8) where Ct (mg/L) is the equilibrium concentration of MB at a

certain time (t). k1 (h− 1), k2 (g/mg.h), and qt (mg/g) are PFO
RT rate constant, PSO rate constant, and adsorption capacity at
β =  (9)
bT time (t), respectively. α (mg/g.h) and β (g/mg) are the initial
rate of MB adsorption and activation energy of adsorption,
where R is the gas constant (8.314 J/mol. K), T (K) is the respectively.
Kelvin constant, β is a constant associated with the heat of
adsorption, bT (J/mol) is the Temkin constant, and KT (L/g) 2.7 Thermodynamics for methylene blue
is the Temkin isotherm constant. adsorption

2.5.4 Dubinin-radushkevich adsorption model Thermodynamic parameters such as the change in entropy
(ΔS°), enthalpy (ΔH°), Gibbs free energy (ΔG°), and equi-
The model of Dubinin-Radushkevich (Eq. 10) is employed librium constant (Kd) were evaluated to study the heat of
to distinguish between adsorption on heterogeneous and adsorption, spontaneity, and the ability of MB adsorption
homogeneous surfaces. Compared to the Langmuir type, on the surface of solid adsorbent nanoparticles. Thermody-
this isotherm has a more generic nature and can be repre- namic parameters were determined by using the following
sented by the following linear equation (Hezma, Shaltout equations:
et al. [35]):
Cs
Kd = (17)
Lnqe = LnqDR − KDR ε  2
(10) Ce

∆ Go = ∆ H o − T ∆ S o (18)
 
1
ε = RT Ln 1+ (11)
Ce
∆S 0 ∆H 0
Ln Kd = −  (19)
In this case, qDR and KDR are the maximum capacity of R RT
adsorption (mg/g) and the D–R constant (mol2/kJ2). T, R,
and ε denote Kelvin temperature, the gas constant, and the Herein, Ce and Cs (mg/L) are the equilibrium concentrations
Polanyi potential, respectively. The mean free energy of of MB in the solution and on the surface of the adsorbent,
adsorption (EDR, kJ/mol) is described as: respectively. Kd is related to the distribution equilibrium
constant of adsorption. The Van’t Hoff equation (Eq. 19)
1 enables the calculation of the enthalpy and entropy changes
EDR = √  (12)
2KDR for the adsorption process using the slope and intercept.

2.8 Methylene blue desorption and solid adsorbent

2.6 Adsorption kinetic models reusability

Three adsorption kinetic models were investigated for the For the desorption study, 0.5 g of CSZ as selected solid
rate and mechanism of methylene blue adsorption, namely, adsorbents was mixed with 200 mL of 500 mg/L MB

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1648 Adsorption (2024) 30:1643–1661

solution and agitated for 24 h. After the adsorption equilib- and 800 °C, which is attributed to the formation of residual
rium was established, CSZ was filtered, gently washed with ash content (Saleh, Al-Zaidi and Sabbar [54]). Additionally,
an amount of distilled water to eliminate any residual MB the mass of the nanosilica sample (SN) decreases slowly
and dried at 50 oC. The dried MB pre-loaded CSZ sample by only 5.8% up to 800 °C, which could be caused by the
was shaken with 50 mL of distilled water, 1 mol/L sodium desorption of residual moisture, and this may be due to the
hydroxide, ethanol (97%), benzene, and nitric acid for 24 h high porosity of nanosilica, indicating higher thermal sta-
at 45 oC. The desorbed MB concentration was measured in bility of SN at high temperatures [24]. The polar nature of
solution after filtration. Desorption efficiency (D.E%) was the inorganic functional groups of the nanozeolite-Y (ZN)
calculated using the given Eq. 20 (Daneshvar, Vazirzadeh surface is responsible for its higher level of surface mois-
et al. [12]): ture adsorption. ZN showed another weight loss from 110
to 240 °C due to the evaporation of water molecules trapped
V Cd inside the nanozeolite structure (Hassan, Alafid and Hrdina
D.E% = × 100  (20)
qW [25]. Another stage of mass loss for ZN occurred between
250 and 800 °C, which was associated with thermal degra-
where Cd (mg/L) is the concentration of MB solution after dation of hydroxyl groups. The thermogravimetric curve of
desorption from the surface of CSZ. V (L) is the solution CS showed that 4.1% mass loss occurred in the region of
volume. q (mg/g) is the maximum adsorbent adsorption 110–145 °C because of residual water loss. This high tem-
capacity. W (g) is the adsorbent mass. perature (145 °C) can be responsible for the strong hydro-
Adsorbent regeneration was performed after six cycles gen bonding between water molecules and the active groups
of MB adsorption and desorption runs. Adsorption of MB (-NH2 and -OH) of chitosan. From 295 to 350 °C, the gly-
was tested by CSZ under 2 g/L of adsorbent dose, pH 7, cosidic bonds in chitosan units are degraded, resulting in
500 mg/L as MB concentration, 24 h of shaking time, and a weight loss of 7.6%(Habiba, Siddique et al. [22], Kan-
at 20 °C. After each cycle, the adsorbent was filtered and dile, Ahmed et al. [38]). The CSZ composite had a thermal
cleaned several times with 20 mL of nitric acid to desorb the behavior that was in the middle of ZN and CS solids. This
adsorbed MB and dried at 70 °C for successive reuse. was because ZN was mixed into the structure of CS. The
residual mass for samples at 800 °C, because of the thermal
stability of SN > ZN > CSZ > CS > RH.
3 Results and discussion The nitrogen adsorption and desorption isotherms are
used to examine the structural properties of the synthesized
3.1 Characterization of the solid adsorbents materials, as depicted in Fig. 1b. The solid samples (SN,
ZN, and CSZ) showed a type IV adsorption isotherm based
Thermogravimetric analysis (TGA) is a technique that mea- on the IUPAC classification, where the adsorption process
sures the mass of a sample in dependence on temperature. rises very steeply due to the capillary condensation in meso-
It is particularly effective to examine the thermal stability pores with hysteresis loops of H2 type for ZN and CSZ, but
and purity of solid materials at temperatures ranging from SN displayed a mixture between type H1 and H2 hysteresis
18 to 800 °C. The prepared materials (RH, SN, ZN, CS, and loops [24], Hassan, Alafid and Hrdina [25]. CS showed a
CSZ) displayed a total loss of mass of 73.4, 6.9, 28.2, 65.5, type II without hysteresis loops appeared, which may be
and 55.8%, respectively, at 800 °C, as shown in Fig. 1a. At related to its wide pore diameter (4.41 nm). The findings in
110 °C, all of the samples lost about 3.2% (RH), 1.1% (SN), Table 1 indicate that the specific surface area (SBET) values
6.3% (ZN), 3.8% (CS), and 5.2% (CSZ) wt% of their weight of ZN ˃ SN ˃ CSZ ˃ CS are 857.2, 804.0, 432.3, and 177.7
due to the particles’ pores evaporating water(Shaltout, El- m2/g, respectively, and that observation is evidenced by the
Naggar et al. [55]). RH has a high level of moisture, indicat- total pore volume of ZN ˃ SN ˃ CSZ ˃ CS. The surface area
ing the high availability of hydroxyl functional groups on its of ZN (857.2 m2/g) agrees with its lower TEM particle size,
surface. Severe RH weight loss occurs at about 170 °C and which ranged from 5.8 to 13.9 nm. This is based on the fact
finishes at about 435 °C, and this reduction of about 51.3 wt% that as the size of the crystal in the sample decreases, the
is caused by the hemicellulose and cellulose breaking down external surface area increases(Taufiqurrahmi, Mohamed
and releasing volatiles that are extracted from the organic and Bhatia [58]). Also, as appeared in XRD, the peaks are
components as condensable vapors (acetic acid, methanol, sharp, revealing that ZN has high crystallinity and nano-
and wood tar) and incondensable gases (CO, CO2, CH4, H2, crystal size, resulting in its high surface area(Shaltout, El-
and H2O) released at this point (Saleh, Al-Zaidi and Sabbar Naggar et al. [55]). The CSZ composite has a larger surface
[54], F. Hincapié Rojas, Pineda Gómez and Rosales Rivera area than CS but a smaller surface area than ZN. This is
[20]). The final decomposition of RH occurred between 435 because some of the inter-particle void volume aggregates

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Adsorption (2024) 30:1643–1661 1649

Fig. 1 TGA curves (a), nitrogen adsorption/desorption isotherms (b), XRD (c), FTIR spectra (d), and zeta potential (e) for RH, SN, ZN, CS, and
CSZ

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1650 Adsorption (2024) 30:1643–1661

Table 1 Point of zero charge and textural parameters for SN, ZN, CS, related to the hydroxyl group of water molecules (Edañol,
and CSZ
Usman et al. [16], Hassan, Alafid and Hrdina [25]). The
Samples pHPZC SBET (m2/g) VT (cm3/g) r̄ (nm) pure CS pattern has a broad crystalline band that corre-
SN ----- 804.0 0.581 2.89
sponds to O–H and N–H stretching. N–H and C-O-H bend-
ZN 4.75 857.2 0.584 2.72
ing and C-O-C stretching are related to the different bands at
CS 7.41 177.7 0.196 4.41
CSZ 6.89 432.3 0.280 2.59
1639, 1408, and 1016 cm− 1, respectively (Hassan, El-Aziz
et al. [32]. The broad band at 3425 cm− 1, which is charac-
teristic of chitosan, is attributed to the stretching vibration
are filled(Bortolatto, Boca Santa et al. [9]). The average of the OH group (Habiba, Siddique et al. [22]). Compared
pore diameter ( r, nm ) for CS (4.41 nm) ˃ SN (2.89 nm) ˃ to the spectra of ZN and CS, CSZ illustrated the combina-
−

ZN (2.72 nm) ˃ CSZ (2.59 nm) indicates the mesoporosity tion of absorbance bands between the CS and ZN groups.
of all the samples (Hassan, Alafid and Hrdina [25]. The band at 662 cm− 1 is attributed to the vibration of the
XRD analysis was used to examine the sample nature external linkage between tetrahedral units, and the peak at
and crystal structure of the synthesized adsorbents (SN, ZN, 425 cm− 1 was also observed in the synthesized composite.
CS, and CSZ), as illustrated in Fig. 1c. The X-ray pattern Some of the characteristic bands of CS were shifted from
of the nanosilica portrayed a strong, sharp peak of pure SN 1408 to 3425 cm− 1 to 1415 and 3570 cm− 1, respectively,
centered at 2θ = 21.7°, which is compatible with the peak and the peak at 989 cm− 1 in ZN was shifted to 978 cm− 1
of a characteristic SiO2 with some less intense peaks at in composite. The additional absorption band at 1558 cm− 1
2θ = 28.0o, 29.9o, 31.2o, 36.0o, 42.4o, 44.4o, and 48.3o. The corresponds to O–H, which may be evidence of the mixture
presence of a sharp peak at 21.7o confirms the ordered semi- of nanozeolite and chitosan.
crystalline structure within the generated silica nanoparti- The chemical surface charge analysis was studied
cles. The produced silica nanoparticles appeared to sharpen through the zeta potential measurements, which calcu-
their diffraction peaks due to their smaller particle size and lated the pHPZC (point of zero charge). The pHPZC values in
surface defects [24]. Nanozeolite-Y showed characteristic Table 1 disclose that the pHPZC values of ZN, CS, and CSZ
peaks in a crystalline structure located at 2θ values of 10.1o, are 4.75, 7.41, and 6.89, respectively, at which the surface
11.9o, 15.7o, 18.7o, 20.4o, 23.5o, 27.9o, 31.5o, 34.1o, and has zero charge, as shown in Fig. 1e. Where, at pH values ˂
37.9°. According to the XRD analysis, it appears the FAU pHPZC the surface of the adsorbent carries a positive while
structure of the ZN sample is attributable to the presence of at pH ˃ pHPZC carry a negative charge.
small crystals (Taufiqurrahmi, Mohamed and Bhatia [59]). The surface morphology and shape of the samples (SN,
Two peaks at 2θ = 15.3o and 21.9o corresponding to (240) ZN, CS, and CSZ) were identified by SEM and TEM
and (273), respectively, were visible in the XRD pattern of analysis. The scanning electron microscopy (SEM) micro-
chitosan (CS), which designates the amorphous structure of graphs of the prepared adsorbents are shown in Fig. 2a-d.
the substance (Li, Liu et al. [41]). The CSZ composite is The image of nanosilica is uniformly and homogeneously
similar to ZN in crystallinity, but it showed a decrease in arranged with aggregation [24]. Comparing the analysis of
intensity and shift in peaks compared to ZN, which illus- the SEM micrograph with the results from the XRD pattern
trated an excellent incorporation between ZN and CS. analysis, it was demonstrated that silica is a semi-crystalline
The prepared samples’ chemical bonds and other func- form. ZN showed agglomerated irregular crystals with an
tional groups can be characterized by FTIR analysis. Fig- octahedral form as well as the formation of pores as a result
ure 1d shows the characteristic symmetry peaks of silica at of nuclei growth (Hassan, Alafid and Hrdina [25]. A picture
796 cm− 1 and 952 cm− 1 which can be related to the Si-O- of chitosan revealed typical dome-shaped orifices, a large
Si stretching vibration, and at 452 cm− 1, which belongs to surface area, and micro-fibrils in its smooth and non-porous
the Si-O-Si bending vibration in the SN sample. The strong membranous phase (Sinha, Singh and Dutta [57]). The pre-
and broad peak of asymmetry of Si-O-Si is at 1070 cm− 1 vious characteristics demonstrate the successful encapsula-
[33]. Theoretically, the characteristic absorption bands of tion and good homogeneity of the two solid materials (ZN
nanozeolite (ZN) are around 501, 666, 814, 989, 1628, and and CS). The coordination of the chitosan binding sites with
3351 cm− 1. The peak at 501 cm− 1 is a characteristic vibra- the nanozeolite molecules resulted in a noticeable morpho-
tion of the internal tetrahedrons of zeolite structures, and logical change in the image of the CSZ nanocomposite film.
the peak at 666 cm− 1 is due to the presence of double rings The rough surface of the composite is an important factor in
in the framework, while the peak at 814 cm− 1 is sensitive the adsorption because it contributes to high hydrophilicity.
to the Si-Al network composition. The band at 989 cm− 1 Figure 2e-h show TEM micrographs that provide more
confirms the presence of external asymmetrical stretching precise information on the particle size and surface morphol-
of Si–O. The existence of peaks at 1628 and 3351 cm− 1 is ogy of the produced samples. The shape of the nanosilica

13
Adsorption (2024) 30:1643–1661 1651

Fig. 2 SEM (a-d), and TEM (e-h) images for SN, ZN, CS, and CSZ, respectively

is approximately spheroidal, with an average homogenous there was a higher increase in adsorption capacity with an
particle size distribution of around 30.4–41.8 nm and an increment in the solid dosage from 0.2 for all samples to
irregular geometry of the produced particles (Tolba, Barakat 1.8 g/L for ZN, 1.0 g/L for CS, and 1.4 g/L for CSZ, where
et al. [60]). The TEM image of ZN agreed with the features the adsorption capacity increased from 14.3, 38.6, and 60.0
in the SEM image, with a size of 5.8 to 13.9 nm. Chito- to 64.5, 55.4, and 81.0 mg/g by 4.5, 1.4, and 1.4 times for
san has a fairly uniform and spherical surface shape, with ZN, CS, and CSZ, respectively, because the adsorbent’s
particle sizes ranging from 32.0 to 60.8 nm (Hevira, Ighalo surface-active sites increased as the dosage of the adsorbent
and Sondari [34]). As it appears in the explanation of the rose. After this increase, there was no observed increase in
composite in SEM analysis, the composite shows a particle MB removal, but a decrease occurred at higher adsorbent
size of about 28.6–60.7 nm with white dots, indicating that doses because the active sites of adsorbents may aggregate
nanozeolite particles have interfered with the chitosan struc- during the adsorption reaction, besides the decrease in the
ture, as evidenced by the smaller size of the ZN and the MB/active sites ratio (Ezeh, Ogbu et al. [19]). Based on the
large surface area of chitosan which indicates the strength above results, 2.0 g/L as an adsorbent dose was chosen as
of the new composite. the optimum value for the next experiments.

3.2 Adsorption of methylene blue onto all the 3.2.2 Effect of solution pH
prepared solid adsorbents
The change in MB adsorption capacity for ZN, CS, and CSZ
3.2.1 Effect of nanosolid adsorbent dosage with pH is displayed in Fig. 3b. The results were studied
in a pH range of 2–12 at 20 °C using a 2 g/L adsorbent
The adsorbent dose is an essential effect that can greatly dose and a 300 mg/L initial MB concentration for 24 h of
affect the adsorption of methylene blue on adsorbents. The shaking time. At lower pH levels (pH < pHPZC), all solid
relation between adsorbent dosages (g/L) and the adsorp- adsorbents had low qe values. This was because H+ ions in
tion capacity (qe, mg/g) is shown in Fig. 3a, using a dosage the solution made it hard for the solid adsorbents to bond
range of 0.2 to 2.4 g/L at 20 °C for 24 h of shaking time and with methylene blue. The previous result can be explained
300 mg/L of initial MB concentration. It was observed that on the basis that the hydroxyl group in phase bonded to the

13
1652 Adsorption (2024) 30:1643–1661

Fig. 3 Effect of dosage (a), pH (b), contact shaking time (c), PSO (d), and Elovich (e) plots for the adsorption of MB onto ZN, CS, and CSZ at
20 ℃

13
Adsorption (2024) 30:1643–1661 1653

H+ and became positively charged. Also, the –NH2 in CS saturation of surface-active sites with MB dye. Based on
and CSZ molecules undergo protonation to generate –+NH3, previous results, 12 h was determined to be the ideal adsorp-
making it more difficult for the adsorbents to bind to the tion duration.
methylene blue dye cations. The adsorption capacity of MB Utilizing kinetic models, experimental data has been
increased with increasing pH from 2 to 8 for all samples, tested to determine the mechanism of MB adsorption. The
due to the increase in the electrostatic attraction between parameters of the kinetic models are provided in Table 2.
adsorbent sites and MB dye (Shaltout, El-Naggar et al. The most often employed models are the pseudo-first order
[55]). When the pH was raised from 8 to 12, ZN’s ability (Eq. 13) and pseudo-second order (Eq. 15) models shown
to absorb dye increased by 6.1%. This was because there in Fig. S1 and Fig. 3d, respectively, while the Elovich
were more negatively charged sites on the adsorbent sur- model (Eq. 16) is portrayed in Fig. 3e. According to the
face, which made the dye stick to it better. In general, as the result in Table 2 we can conclude that (i) the adsorption
pH level increased, the net positive charge decreased. This of MB onto ZN, CS, and CSZ did not follow the kinetic
made it easier for the dye to stick to the adsorbent surface, model of PFO because of the large difference between qm
which increased its ability to absorb dye [17]. In the case of (Langmuir adsorption capacity) and qexp (adsorption capac-
CS and CSZ, MB adsorption decreased significantly with an ity calculated from PFO) values, and the percentage differ-
increase in pH from 8 to 12 due to an increase in the number ence between them is 61.7, 38.0 and 16.6% for ZN, CS,
of negative hydroxide ions that compete with adsorbents for and CSZ, respectively. However, the correlation coefficients
the adsorption of methylene blue dye (Anvari, Hosseini et (R2, 0.9351–0.9646) are high but less than the correlation
al. [8]). The maximal adsorption capacity for CSZ at pH7 is coefficient for PSO. (ii) The adsorption of MB onto all three
about 98% at pH 7.9, indicating that the two values are not solid adsorbents fitted well to the PSO kinetic model based
significantly different. Accordingly, pH = 7 was selected as on its higher R2 from 0.9985 to 0.9997 and the closer degree
the optimum pH value for MB adsorption onto all the inves- between qm and qexp values by a percentage difference of
tigated solid samples. only 2.8–6.1%.
(iii) The rate constant (k2) for PSO followed the sequence:
3.2.3 Effect of time and kinetic study ZN (0.0268 g/mg.h) > CS (0.0139 g/mg.h) > CSZ (0.0049 g/
mg.h), which may be associated with the strong attraction
As shown in Fig. 3c, the plot between adsorption capacity between ZN and MB. (iv) The correlation coefficients of
and time determines the shortest time needed for the adsor- the Elovich kinetic model were more than 0.9618, revealing
bent process. The contact shaking time was varied from the good applicability of this model. Also, the initial rates
0.25 to 25 h at 2 g/L of adsorbent dose, pH 7, 300 mg/L (α) and the extent of surface coverage (β) sequence of MB
initial dye concentration, and 20 °C. All solid adsorbents adsorption followed the following sequence of ZN ˃ CS ˃
displayed a high initial rate of MB adsorption, which CSZ, indicating an increase in the adsorption equilibrium
increased from 1 to 12 h due to the presence of numerous and surface coverage (Inyinbor, Adekola and Olatunji [36],
active sites on their surface. The adsorption rate was slowed Alene, Abate and Habte [7], Hassan, Mustafa et al. [31]).
down and remained unchanged from 14.0 to 25 h due to the Based on the previous study, we can conclude that the

Table 2 PFO, PSO, and Elovich Models Parameters ZN CS CSZ

kinetic models and thermody- qm(mg/g) 78.989 58.997 84.746
namic parameters for the MB
adsorption onto ZN, CS, and CSZ PFO qexp(mg/g) 30.280 36.564 70.640
samples k1(h− 1) 0.3352 0.3260 0.2723
R2 0.9429 0.9351 0.9646
PSO qexp(mg/g) 74.202 60.643 89.251
k2(g/mg.h) 0.0268 0.0139 0.0049
R2 0.9997 0.9992 0.9985
Elovich α (mg/g.h) 24736.5 430.8 93.3
β (g/mg) 0.1536 0.1161 0.0502
R2 0.9843 0.9618 0.9848
Thermodynamic parameters R2 0.9972 0.9540 0.9894
ΔHo(kJ/mol) -14.1577 12.4306 8.5946
ΔSo(kJ/mol.K) -0.0511 0.0442 0.0314
‒ΔGo(kJ/mol) 20 ℃ -0.8240 0.5186 0.6194
30 ℃ -1.3353 0.9605 0.9338
40 ℃ -1.8466 1.4024 1.2483
47 ℃ -2.2046 1.7118 1.4684

13
1654 Adsorption (2024) 30:1643–1661

adsorption of MB onto all solids fits well with the PSO and Freundlich (R2 > 0.9348) model based on the higher correla-
Elovich models, besides the strong attraction towards the tion coefficient of the Langmuir model (Hassan, El-Naggar
nanozeolite-Y surface. et al. [27] Hassan, El-Naggar et al. [28]. The effect of tem-
perature on Langmuir and Freundlich isotherms from 20
3.2.4 Effect of the initial concentration of MB and to 47 °C explained that MB adsorption is endothermic on
adsorption isotherms the CS and CSZ surface, while MB adsorption onto the ZN
surface is exothermic. CSZ adsorption capacity was higher
than ZN by 7.3, 107.6, 167.4, and 190.2% at 20, 30, 40, and
Methylene blue dye adsorption onto the solid adsor- 47 °C, respectively; this is because the CSZ surface has a
bents at 20, 30, 40, and 47 °C was studied using a higher total pore volume, specific surface area, and rich new
2 g/L adsorbent dose and 25–700 mg/L as the initial surface chemical functional groups, which contribute to
MB concentration at pH 7 for 12 h as shaking time. attracting MB cations and resulting in an enhanced adsorp-
The effect of starting concentration of MB on the tion process (Hassan, Mustafa et al. [31]. Langmuir bind-
adsorption capacity of ZN, CS, and CSZ is illustrated ing constant value (KL, L/mg) was higher in CSZ than those
in Fig. 4a-c, which shows that the rate of MB adsorp- in ZN and CS, revealing the higher binding force between
tion was very high at lower initial concentrations due the CSZ surface and MB molecules. The good favorability
to a lower number of MB cations to active sites for of MB adsorption onto ZN, CS, and CSZ was indicated by
all adsorbents but eventually became stable at higher the RL values from 0.0575 to 0.4064, as shown in Table 3.
initial concentrations, which could be related to active Additionally, the physical and favorable adsorption process
site saturation. The results in Fig. 4a-c indicate that of MB was confirmed by the analyzed 1/n values, which
the adsorption capacity increases with an increase in ranged between 0.1653 and 0.6370 (0.1 < 1/n < 1.0) (Has-
temperature, which indicates the endothermic nature san, Alshandoudi and Shaltout [26].
in the case of both CS and CSZ. On the other hand, Linear Temkin and Dubinin-Radushkevich (D-R) plots
increasing the temperature reduced the adsorption for MB adsorption onto ZN, CS, and CSZ at 20, 30, 40,
capacity of ZN, indicating that the adsorption process and 47 ℃ are shown in Fig. 5a- c and d-f, respectively, and
is exothermic due to the weakening of the attractive their obtained data are found in Table 3. Concerning the
forces between the MB dye and the active sites on the results shown in Table 3, (i) these models well also applied
adsorbent surface and the fact that an increase in the the adsorption of MB onto ZN, CS, and CSZ according
temperature of the liquid phase will increase the solu- to the larger R2 values (0.9319 − 0.9993) for the Temkin
bility of the adsorbate molecules as well as their diffu- model and (0.9121–0.9981) for the Dubinin-Radushkevich
sion inside the adsorbent pores. Indeed, the adsorption model. (ii) The range of the Temkin parameter values (bT
of MB on the ZN surface is favourable at low tem- < 8000 J/mol) from 91.55 to 446.66 J/mol demonstrated
peratures (Al-Aoh, Mihaina et al. [6], [5], Salahshour, the dominance of physical adsorption. (iii) The small dif-
Shanbedi and Esmaeili [53]). ference between (qm, mg/g) from the Langmuir model and
calculated (qDR, mg/g) from Dubinin-Radushkevich, which
Various adsorption isotherm models have been used to ranged between 0.02 and 20.66%, supported the good appli-
test the isotherms of Langmuir (Eq. 5), Freundlich (Eq. 7), cation of the D-R model. According to the assessed EDR val-
Temkin (Eq. 8), and Dubinin-Radushkevich (Eq. 10), while ues (< 0.0387 kJ/mol), MB is physiosorbed onto ZN, CS,
the calculated parameters are illustrated in Table 3. Lin- and CSZ, where chemisorption and physisorption processes
ear Langmuir model and Freundlich model plots for MB are accomplished for 8 ˂ EDR < 16 kJ/mol and EDR ˂ 8 kJ/
adsorption onto ZN, CS, and CSZ at 20, 30, 40, and 47 ℃ mol, respectively (Hassan, El-Naggar et al. [27]).
are shown in Fig. 4d-f and Figs. S2a-c, respectively, and
the obtained data are listed in Table 3. The results data dis- 3.2.5 Effect of temperature and thermodynamic
cussed the higher correlation coefficients from 0.9680 to parameters
0.9972 for the Langmuir model and from 0.9348 to 0.9787
for Freundlich. The adsorption of MB onto all the produced Adsorption of MB onto all the prepared solid materials was
solid samples applied well with the Langmuir and Freun- studied at four temperatures (20, 30, 40, and 47 °C) with an
dlich adsorption models, indicating the growth of homoge- initial concentration of 300 mg/L of dye solution, an amount
neous monolayer and heterogeneous multilayer adsorption of adsorbent of 2 g/L, pH 7, and 12 h as shaking time, and the
of MB on active sites of solid surfaces. But comparing the results are shown in Fig. 6a; Table 2. Exothermic or endo-
Langmuir and Freundlich models we can conclude that the thermic processes can be determined with their positive or
Langmuir (R2 > 0.9680) model is more applicable than the negative enthalpy values (ΔHo)(Doan [14]. The results from

13
Adsorption (2024) 30:1643–1661 1655

Fig. 4 Adsorption isotherms of MB (a-c) and Langmuir plots (d-f) for ZN, CS, and CSZ, respectively at 20, 30, 40, and 47 ℃

13
1656 Adsorption (2024) 30:1643–1661

Table 2 show that the higher correlation coefficient values of

141.04
0.0292
0.2549
0.9906

0.2890
24.603
0.9446

0.3679
100.09
0.9853

134.35
0.0273
0.9881
47 oC the Van’t Hoff plot (Eq. 19) for ZN (0.9972), CS (0.9540),
and CSZ (0.9894) indicate the good fit of this model as pre-
sented in Fig. 6a. The ΔHo values are − 14.1577, 12.4306,
and 8.5946 kJ/mol for ZN, CS, and CSZ, respectively, con-
123.92
0.0393
0.2028
0.9938

0.2305
30.974
0.9560

1.1521
135.97
0.9527

0.0301
0.9724
119.90
40 oC

firming the exothermic nature of ZN and the endothermic

nature of CS and CSZ for MB adsorption onto the prepared
samples. The ΔS° values are 0.0442 kJ/mol.K for CS and
Table 3 Adsorption parameters of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich for the adsorption of MB onto ZN, CS, and CSZ at 20, 30, 40, and 47 ℃

0.0314 kJ/mol.K for CSZ. This means that there was more
0.0403
0.1988
0.9904

0.2975
20.229
0.9668

0.5443

0.9845

0.0220
0.9972
117.51

119.69

118.86
30 oC

randomness at the interface between adsorbent and solution

during the adsorption process. On the other hand, the ZN
value went down by -0.0511 kJ/mol.K, which showed the
opposite situation (Al-Aoh, Mihaina et al. [6]). The posi-
0.0807

0.9957

0.1949

0.9685

3.9793
209.35
0.9624

0.0387
0.9968
0.1102

28.111
20 oC

84.76

83.42
CSZ

tive values of ΔGo for ZN range from 0.8240 to 2.2046 kJ/

mol, proving the nonspontaneous nature of MB adsorption
onto the ZN surface, and ΔGo for CS and CSZ range from
103.63
0.0262
0.2761
0.9680

0.3505
12.966
0.9580

0.3308
142.45
0.9709

0.0382
0.9567
− 0.5186 to -1.7118 kJ/mol, confirming the spontaneous
47 oC

85.92

nature of MB adsorption (Hassan, El-Naggar et al. [27]).

Nonspontaneous adsorption of MB on ZN implies that the
adsorption process requires extra power to increase the
0.0146
0.4064
0.9777

0.3959

0.9787

0.2952
153.32
0.9615

0.0298
0.9360

adsorption efficiency.
40 oC

95.69

8.522

75.92

3.3 Desorption and reusability studies

0.0241
0.2930
0.9962

0.3130
10.226
0.9693

0.4880
214.84
0.9699

0.0182
0.9844

Desorption studies have provided a qualitative analysis of

30 oC

69.44

67.80

the reversibility of the adsorption process. Figure 6b dem-

onstrates the use of several eluents for MB desorption from
the CSZ adsorbent. The desorption efficiency was calcu-
0.0261
0.2771
0.9924

0.2808
10.051
0.9665

0.7652
266.08
0.9809

0.0143
0.9759

lated using Eq. 20, showing the following trend: nitric

20 oC

58.99

58.98
CS

acid ˃ sodium hydroxide ˃ ethanol ˃ benzene ˃ distilled

water, with percentages desorption of 99, 29, 13, 8, and 6%,
respectively. Viscosity, eluent polarity, solubility of MB in
0.0128

0.9903

0.4510

0.9348

0.1239
242.45
0.9319

0.0245
0.9981
0.1121
47 oC

48.60

3.182

43.02

eluent, and the number of cations (especially protons) pro-

duced from desorbing eluent determine the desorption effi-
ciency values. Nitric acid achieved high desorption of MB,
leading to a significant electrostatic repulsion between the
0.0591
0.0575
0.9972

0.1653
16.961
0.9565

5.6756
446.66
0.9810

0.0260
0.9520
40 oC

46.34

46.93

highly protonated CSZ surface and the MB cations. Dis-

tilled water and benzene showed the lowest desorption per-
centages, which are due to the small number of positively
charged protons produced (Daneshvar, Vazirzadeh et al.
0.0544
0.0693
0.9953

0.2614
12.252
0.9569

0.8832
272.22
0.9461

0.0334
0.9121
30 oC

56.59

54.85

[12], Ahmad and Ejaz [3]. The reuse study was performed
in six adsorption/desorption cycles and removal efficiency
was determined in each cycle. The data also explained
that the MB adsorption efficiency of the CSZ composite
0.0957
0.9957

0.6370

0.9670

0.0497

0.9993

0.0239
0.9757
0.0117
20 oC

78.99

2.123

91.55

69.94

slightly decreased by 9.5% after six cycles used for MB dye

ZN

removal, as shown in Fig. S3, and that may be attributed

Dubinin-Radushkevich

to the CSZ particles’ coagulation, resulting in a reduction

in surface area and the loss of some chemical functional
KF(L1/n. mg1 − 1/n/g)

groups. The regeneration results show that the composite

adsorbent maintains its high adsorption efficiency for MB
EDR(kJ/mol)
Parameters

Freundlich
Langmuir

qDR(mg/g)
KL(L/mg)

bT(J/mol)

even after numerous recycles [17].

qm(mg/g)

Temkin
KT(L/g)
1/n
RL
R2

R2

R2

R2

13
Adsorption (2024) 30:1643–1661 1657

Fig. 5 Temkin (a-c) and linear Dubinin–Radushkevich plots (d-f) for the adsorption of MB onto ZN, CS, and CSZ, respectively at 20, 30, 40, and
47 ℃

13
1658 Adsorption (2024) 30:1643–1661

Fig. 6 Van’t Hoff plot for all the studied solid adsorbents (a) and desorption of MB from CSZ using different solvents (b)

Table 4 Maximum adsorption capacity of CSZ in comparison to other functional groups, and crystalline structure. Sample dose,
composites shaking time, pH, starting MB concentration, temperature, and
Adsorbents qm (mg/g) references other essential experimental parameters were established, and
CZC 24.5 [60] experimental results have been recorded. Adsorption of MB
Fe3O4/ZA 40.4 [61] onto all the prepared solid materials was investigated, where
CCM 45.1 [62]
CSZ exhibited higher adsorption capacities towards MB dye
Chitosan-magadiite beads 45.3 [63]
and increased from 84.76 to 141.04 mg/g by raising the tem-
Zeolite–rGO 53.3 [64]
perature from 20 to 47 °C, utilizing 2 g/L of adsorbent dos-
Zeolite/AC@MnO2 67.6 [65]
CS–ZX aerogels 108.0 [66] age, 12 h of shaking time, and pH 7. Kinetic studies prove the
CSZ 141.0 [This study] good applications of PSO and Elovich models. The Langmuir,
Freundlich, Temkin, and Dubinin-Radushkevich adsorption
isotherms were good at describing how MB stuck to all the
3.4 Comparison of CSZ with other adsorbents solid adsorbents that were made. Thermodynamic studies
showed that MB spontaneously and endothermically attached
In this study, CSZ was compared with other solid materials to CS and CSZ, but ZN did not adhere spontaneously and exo-
for MB adsorption, as shown in Table 4 (Zhu, Wang et al. thermically. Nitric acid played an essential role in the desorp-
[66], Cho, Jeon et al. [11], Dehghani, Dehghan et al. [13], tion of MB from the solid surface by about 99%. The higher
Mokhtar, Abdelkrim et al. [44] Marotta, Luzzi et al. [43], reusability of CSZ was tested after six cycles of MB adsorp-
Tran, Duong et al. [62], Shojaei and Esmaeili [56]. We found tion and desorption and exhibited a decrease in its adsorp-
that CSZ had the greatest adsorption capacity compared to tion capacity of only 9.5%. Lastly, methylene blue and other
the other materials, showing that CSZ is an excellent solid organic colors may be effectively removed from wastewater
adsorbent for MB removal from aqueous solutions. using the CSZ composite made of nanozeolite Y and chitosan.

Supplementary Information The online version contains

supplementary material available at https://doi.org/10.1007/s10450-
4 Conclusion 024-00527-x.

In summary, rice husks were used to synthesize silica nanopar- Author contributions S.A.E. conducted the primary research, includ-
ticles which were used in the preparation of nanozeolite- ing synthesis, characterization, and experiments. A.G.B. assisted with the
Y (ZN) and nanozeolite-Y/chitosan composite (CSZ) was experimental work and characterization techniques and wrote the initial
draft. A.F.H. and M.M.T.E. co-supervised the project, provided guidance
resulted from the combination of the ZN nanoparticles and on experimental design, and contributed to the interpretation of data. They
the prepared chitosan (CS). Characterization investigations by also co-wrote and revised the manuscript.
different techniques: TGA, nitrogen adsorption, SEM, TEM,
FTIR, XRD, and Zeta potential showed CSZ composite with a Funding Open access funding provided by The Science, Technology &
total mass loss of 55.8% at 800 °C, higher surface area (432.3 Innovation Funding Authority (STDF) in cooperation with The Egyptian
Knowledge Bank (EKB).
m2/g), pHPZC (6.89), porous structure, richness with chemical

13
Adsorption (2024) 30:1643–1661 1659

Data availability No datasets were generated or analysed during the Ash as Economical Alternative Bioadsorbent. J. Chem. 2020,
current study. 1–11 (2020)
8 Anvari, S., Hosseini, M., Jahanshahi, M., Banisheykholeslami,
F.: Design of chitosan/boehmite biocomposite for the removal
Declarations of anionic and nonionic dyes from aqueous solutions: Adsorp-
tion isotherms, kinetics, and thermodynamics studies. Int. J. Biol.
Ethical approval Not applicable. Macromol. 259(Pt 2), 129219 (2024)
9 Bortolatto, L.B., Boca Santa, R.A.A., Moreira, J.C., Machado,
Competing interests The authors declare no competing interests. D.B., Martins, M.A.P.M., Fiori, M.A., Kuhnen, N.C., Riella,
H.G.: Synthesis and characterization of Y zeolites from alterna-
Novelty Our manuscript introduces novel findings that advance the tive silicon and aluminium sources. Microporous Mesoporous
synthesis and characterization of solid adsorbents, specifically nanoze- Mater. 248, 214–221 (2017)
olite-Y, chitosan, and their composite. We demonstrate their effective 10 Boycheva, S., Marinov, I., Miteva, S., Zgureva, D.: Conversion
application in removing methylene blue dye from wastewater, provid- of coal fly ash into nanozeolite Na-X by applying ultrasound
ing fresh insights that are poised to influence future research and ap- assisted hydrothermal and fusion-hydrothermal alkaline activa-
plications. tion. Sustainable Chem. Pharm. 15, 100217 (2020)
11 Cho, D.-W., Jeon, B.-H., Chon, C.-M., Schwartz, F.W., Jeong,
Open Access This article is licensed under a Creative Commons Y., Song, H.: Magnetic chitosan composite for adsorption of cat-
Attribution 4.0 International License, which permits use, sharing, ionic and anionic dyes in aqueous solution. J. Ind. Eng. Chem. 28,
adaptation, distribution and reproduction in any medium or format, 60–66 (2015)
as long as you give appropriate credit to the original author(s) and the 12 Daneshvar, E., Vazirzadeh, A., Niazi, A., Kousha, M., Naushad,
source, provide a link to the Creative Commons licence, and indicate M., Bhatnagar, A.: Desorption of Methylene blue dye from brown
if changes were made. The images or other third party material in this macroalga: Effects of operating parameters, isotherm study and
article are included in the article’s Creative Commons licence, unless kinetic modeling. J. Clean. Prod. 152, 443–453 (2017)
indicated otherwise in a credit line to the material. If material is not 13 Dehghani, M.H., Dehghan, A., Alidadi, H., Dolatabadi, M., Meh-
included in the article’s Creative Commons licence and your intended rabpour, M., Converti, A.: Removal of methylene blue dye from
use is not permitted by statutory regulation or exceeds the permitted aqueous solutions by a new chitosan/zeolite composite from
use, you will need to obtain permission directly from the copyright shrimp waste: Kinetic and equilibrium study. Korean J. Chem.
holder. To view a copy of this licence, visit http://creativecommons. Eng. 34(6), 1699–1707 (2017)
org/licenses/by/4.0/. 14 Doan, L.: Modifying Superparamagnetic Iron Oxide nanoparti-
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