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Zwitterion composite chitosan-epichlorohydrin/zeolite for

adsorption of methylene blue and reactive red 120 dyes

Ali H. Jawad, Ahmed Saud Abdulhameed, Reghioua Abdallah,

Zaher Mundher Yaseen

PII: S0141-8130(20)33759-4
DOI: https://doi.org/10.1016/j.ijbiomac.2020.07.014
Reference: BIOMAC 16062

To appear in: International Journal of Biological Macromolecules

Received date: 23 May 2020

Revised date: 30 June 2020
Accepted date: 2 July 2020

Please cite this article as: A.H. Jawad, A.S. Abdulhameed, R. Abdallah, et al., Zwitterion
composite chitosan-epichlorohydrin/zeolite for adsorption of methylene blue and reactive
red 120 dyes, International Journal of Biological Macromolecules (2020), https://doi.org/
10.1016/j.ijbiomac.2020.07.014

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© 2020 Published by Elsevier.

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Zwitterion composite chitosan-epichlorohydrin/zeolite for adsorption of

methylene blue and reactive red 120 dyes
Ali H. Jawada,*, Ahmed Saud Abdulhameedc, Reghioua Abdallaha,b , Zaher Mundher Yaseend
a
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor,
MALAYSIA
b
Faculty of Technology, University of El Oued, 39000 El Oued, Algeria
c
Chemistry Department, College of Science, University of Anbar, Ramadi, IRAQ
d
Institute of Research and Development, Duy Tan University, Da Nang 550000, Vietnam

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Corresponding author:

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E-mail: ali288@uitm.edu.my; ahjm72@gmail.com (Ali H. Jawad)

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Abstract: In this research, an attempt to develop zwitterion composite adsorbent is conducted by

modifying chitosan (CHS) with a covalent cross-linker (epichlorohydrin, ECH) and an

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aluminosilicate mineral (zeolite, ZL). The zwitterion composite adsorbent of chitosan-
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epichlorohydrin/zeolite (CHS-ECH/ZL) is performed multifunctional tasks by removing two

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structurally different cationic (methylene blue dye, MB), and anionic (reactive red 120 dye,

RR120) dyes from aqueous solutions. The surface property, crystallinity, morphology,
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functionality, and charge of the CHS-ECH/ZL are analyzed using BET, XRD, SEM, FTIR, and
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pHpzc, analyses. The influence of pertinent parameters namely CHS-ECH/ZL dosage (0.02-0.5

g), solution pH (4-10), temperature (303-323 K), initial dye concertation (30-400 mg/L), and

contact time (0-600 min) on the MB and RR120 removal are tested. The research findings

revealed that the adsorption isotherm at equilibrium well explained in according to the

Freundlich isotherm model, and the recorded adsorption capacities of CHS-ECH/ZL are 156.1

and 284.2 mg/g for MB and RR120 respectively at 30 ˚C. The mechanism of MB and RR120

adsorption onto the CHS-ECH/ZL indicates various types of interactions namely, electrostatic

interaction, hydrogen bonding, and Yoshida H-bonding in addition to n-π interaction. Overall,

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this research introduces CHS-ECH/ZL composite as an eco-friendly zwitterion adsorbent with

good applicability towards the two structurally different cationic and anionic dyes from aqueous

environment.

Keywords: Chitosan; Zeolite; Epichlorohydrin; Methylene blue; Reactive red 120; Adsorption

mechanism

1. Introduction

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Nowadays, various industrial sectors such as textile, tanning, leather, plastics, paper,

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pharmaceutical, cosmetics, and rubber are involved in generating a large amount of colored dye

effluents [1]. The effluents discharge containing organic dyes into water bodies leads to
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significant variation in its characteristics such as color, pH, and chemical oxygen demand
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(COD), in addition to harmful effects on human health [2]. Among several cationic dyes,
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methylene blue dye (MB) is the most famous one, which causes several problems on human

heath such as dermatitis, jaundice, vomiting, nausea, allergies, mutations, and heart defects in
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addition to its risks on aquatic organisms [3]. Reactive red 120 (RR120) dye is one of the
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common anionic dyes that contains the azo (-N=N-) groups within the structure, making it low
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biodegradability, thus it can be formed many risks on eco-system, and human health [4].

Consequently, the removal of these dyes from effluents before discharging them into aquatic

systems is extremely important to protect human health and the eco-system. Various chemical,

physical, and biological approaches such as adsorption [5], nanofiltration [6], photodegradation

[7], and catalytic ozonation [8] have been applied to remediate organic dyes from effluents. The

adsorption is one of the effective methods among all the forgoing methods owing to its modeling

potential, low cost, easy to operate, high efficiency, produce lower waste and non-susceptibility

to pollutants [9]. Composites based-biopolymer are one the most adsorbent applied in

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wastewater treatment due to its desirable properties such as abundant functional groups,

biocompatibility, environmentally friendly, high adsorption capacity, chemical stability,

biodegradability, antibacterial properties and non-toxicity [10-16].

Chitosan (CHS) is a cationic biopolymer of D-glucosamine units, and formed from

alkaline N-deacetylation of chitin, which is existed in the shells of crustaceans, insects etc [17].

CHS has several of outstanding chemical and biological properties such as biocompatibility, high

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chemical reactivity, non-toxicity, biodegradability, hydrophilicity, adsorption capacity, chelation,

chirality, and antimicrobial activity [18]. CHS is distinguished in existence of the hydroxyl (-

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OH) and amino (-NH2) groups in its chain, which acts as the potential adsorption sites to uptake

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several water pollutants such as pharmaceuticals, dyes and metal ions [19]. Nonetheless, pristine
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CHS based adsorbents are mostly pH sensitive, mechanically unstable, and susceptible to
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swelling [20]. Hence, it is essential to evolve the adsorption, surface area, and chemical stability

properties of CHS biopolymer. Many strategies have been applied to develop the
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physicochemical properties of CHS such as crosslinking reaction [21], grafting [22], and
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compositing [23]. Among these strategies, crosslinking reaction is the most favourable method

for improving properties of CHS in terms of solubility in acidic medium, hydrophobicity,

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mechanical stability, and chemical stability [24]. The crosslinked CHS adsorbents have been

widely applied to remove of dyes from aqueous solutions [25].

The approach of CHS-based composites has attracted great attention due to its impressive

properties such as surface area, chemical stability, mechanical strength, and structural properties

[26]. Various fascinating materials such as graphene oxide [27], MgO [28], and zeolite [29] have

been used in preparation CHS composites to enhance its properties including physiochemical and

adsorption capability. Zeolite (ZL) is one the most common porous adsorbents, which is mainly

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composed of aluminosilicate minerals [30]. ZL offers various features when utilized as adsorbent

solo and/or within CHS composite in the removal of water pollutants such as high chemical,

surface area, variety of structural properties, low cost, good mechanical stability, and high

adsorption capacity towards cations species [31]. CHS-ZL composites are receiving increased

attention in the field of pollutants removal from water/wastewater, i.e. adsorption of methyl

orange [32], removal of Cr (VI), Fe (III), and Ni (II) ions [33], and adsorption of humic acid

[34].

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To the best knowledge of the current research, the exploration of new zwitterion

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composite adsorbent of chitosan-epichlorohydrin/zeolite (CHS-ECH/ZL) adsorbent was

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investigated to offer a multifunctional adsorptive performances towards two structurally different
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cationic (methylene blue dye, MB), and anionic (reactive red 120 dye, RR120) dyes from

aqueous solutions. The influence of adsorption key pertinent parameters, i.e. CHS-ECH/ZL
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dosage, solution pH, temperature, initial dye concertation and contact time on the removal of
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MB and RR120 were investigated. The adsorption kinetics, isotherms, and mechanism of MB

and RR120 by CHS-ECH/ZL were investigated.

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2. Materials and methods

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2.1 Materials

Chitosan (CHS, deacetylation ≥75 %; medium MW), and zeolite (ZL, type A) were

purchased from Sigma–Aldrich. Epichlorohydrin (ECH) solution was obtained from Fluka.

RR120 dye (MW: 1469.34 g/mol, λmax = 534 nm) was obtained from ACROS, Organics. MB dye

(MW: 319.86 g/mol, λmax = 661 nm, assay: 99%), and acetic acid (CH3COOH) were obtained

from R&M Chemicals. All the reagents and solutions were prepared by using ultrapure water.

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2.2 Synthesis of CHS-ECH/ZL

The CHS-ECH/ZL was prepared by mixing 1 g CHS flakes and 1 g ZL powder (1g

CHS:1g ZL was pre-determined as the best mixing ratio) before being placed in beaker

containing 75 mL of acetic acid solution (5% v/v) under vigorous stirring at room temperature

for 24 h to obtain homogenous viscous solution of CHS-ZL gel. After that, the CHS-ZL gel was

sonicated inside an ultrasonic bath for 30 min to ensure equal and perfect distribution of ZL

particles into polymeric matrix of CHS. Then, the viscous solution of CHS/ZL was converted

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into a bead form by injection of CHS/ZL viscous solution as drops using syringe needle (10 mL)

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into beaker containing 1000 mL of sodium hydroxide solution (0.5 M). The CHS/ZL beads were

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washed with deionized water to remove any residual of sodium hydroxide. The cross-linking
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reaction step was performed by adding of 2 % ECH (40 mL) to the CHS/ZL beads under gentle

stirring inside a thermostat water bath shaker for 2 h at 40 °C. After that, the prepared CHS-
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ECH/ZL beads were washed exhaustively with deionized water and air dried for 24 h. After that,
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the CHS-ECH/ZL beads were ground and dried continuously inside an oven for 24h at 60 ˚C.

Eventually, the CHS-ECH/ZL sample was further ground to obtain a final particle size ≤ 250 µm
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for further MB and RR120 removal applications. The synthesis steps of CHS-ECH/ZL are
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summarized in Fig. 1.

2.3 Characterization

The specific surface area and porosity of CHS-ECH/ZL were measured by N2

adsorption/desorption isotherms at 77 K utilizing Micromeritics ASAP 2060 analyzer. The

morphology of CHS-ECH/ZL and CHS-ECH/ZL after MB and RR120 uptake was determined

using Zeiss Supra 40 VP scanning electron microscopy (SEM). The crystalline structure of ZL

and CHS-ECH/ZL was determined using X-ray diffractometer (XRD, X’Pert PRO, PAnalytical).

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The zero point of charge (pHpzc) of the CHS-ECH/ZL was determined according to the method

described in the literature [35]. The surface functional groups of the CHS-ECH/ZL before and

after MB and RR120 uptake were determined by use of a Fourier transform infrared (FTIR)

spectrophotometer (Perkin-Elmer, Spectrum RX I).

2.4 Adsorption of MB and RR120 by CHS-ECH/ZL

The uptake of MB and RR120 dyes onto CHS-ECH/ZL surface was studied in batch

mode. A specified quantity of adsorbent (0.02 g to 0.5 g) was taken in a set of Erlenmeyer flasks

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(250 mL) comprising of 100 mL of dye (MB or RR120) solution with variety of initial dye

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concentrations (30-400 mg/L) at different levels of pH (4-10). These flasks were placed inside a

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thermostat water bath shaker (WNB7-45, Memmert, Germany) and agitated at fixed shaking
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speed of 110 strokes/min. The MB and RR120 concentrations were measured by UV-Vis

spectroscopy (HACH DR 2800) at the maximum absorbing wavelength (λmax) of 661 nm and 534
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nm, respectively. The MB and RR120 removal (DR %), and adsorption capacity of CHS-
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ECH/ZL towards MB and RR120 at equilibrium, 𝑞𝑒 (mg/g) were calculated by Eq. 1 and Eq. 2,

respectively.
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(𝐶𝑜 − 𝐶𝑒 )
𝐷𝑅 % = × 100 (1)
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𝐶𝑜

(𝐶𝑜 − 𝐶𝑒 )𝑉
𝑞𝑒 = (2)
𝑊

Where 𝐶𝑜 (mg/L) and 𝐶𝑒 (mg/L) are concentrations of dye at beginning, and equilibrium,

respectively; whereas, V (L) represents the volume of dye solution, and W (g) is the amount of

CHS-ECH/ZL.

3. Results and Discussion

3.1. Characterization of CHS-ECH/ZL

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The physicochemical properties of CHS-ECH/ZL are given in Table 1. The BET analysis

showed that the CHS-ECH/ZL has surface area of 1.42 (m²/g), while mean pore diameter was

32.0 nm. The result shows that the surface area of CHS-ECH/ZL was improved compared to the

CHS-ECH without ZL (0.70 m²/g) as reported in our previous study [36]. This observation can

be attributed to loading of ZL particles into polymeric matrix of CHS-ECH is responsible for

enhancing the surface area of CHS-ECH/ZL composite. Consequently, CHS-ECH/ZL is a

mesoporous material (mean pore diameter 2-50 nm) according to the IUPAC classification

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(USA) [37], where the mean pore diameter of the CHS-ECH/ZL is apparently greater than the

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MB and RR120 molecules, suggesting that the MB and RR120 molecules can be entered the

pores of CHS-ECH/ZL easily.

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The XRD patterns of the ZL and CHS-ECH/ZL are provided in Fig. 2. The XRD pattern of
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ZL (Fig. 2a) displays major diffraction peaks at 2θ=12.3°, 15.9°, 23.8°, 25.6°, 26,2°, 27,4°,

29.8°, and 34.03° corresponding to the crystalline structure of ZL as follows: zeolite,

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hydroxysodalite, mullite, quartz, and calcite [38, 39]. The XRD pattern of CHS-ECH/ZL (Fig.
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2b) displays a sharp characteristic diffraction peak at 2θ=22°, 38°, 44°, 65°, and 77°. This

finding illustrates disappearance of the characteristic diffraction peaks of ZL in CHS-ECH/ZL,

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indicating to the chemical interactions between ZL and CHS. Furthermore, this result evidences

that the distribution and compositing of ZL particles into the molecular structure of CHS-

ECH/ZL. This result also indicates that the high crystallinity of CHS-ECH/ZL resulting from

intra-molecular hydrogen bonding between CHS and ZL [40].

FTIR spectra of CHS-ECH/ZL and CHS-ECH/ZL after MB and RR120 uptake are

provided in Fig. 3a-c, respectively. The FTIR spectrum of CHS-ECH/ZL (Fig. 3a) displays

major characteristic peaks at 3447 cm−1, 1659 cm-1, and 1080 cm-1, which can be assigned to

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vibrations of –OH and –NH2, bending vibration of N-H, and stretching vibration of Si-O [41,

42]. The peaks at 2929 cm-1, 1420 cm-1, 1378 cm-1, and 500-650 cm-1 are assigned to the

stretching vibrations of C-H symmetrical and asymmetrical, stretching vibration of C-O,

stretching vibration of C-N, and bending vibrations of Al-O-Si and Si-O-Si, respectively [41,

43]. The peaks at 1150 cm-1 and 1040 cm-1 are correspond to stretching vibration of C-O-C and

C-O bonds respectively, demonstrating that ECH reacts with the carbon atoms of the hydroxyl

groups of CHS to form covalent bonds, causing in the opening of the epoxide ring of ECH and

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the releasing of a chlorine atom [44]. The broad band at 3400 cm-1 corresponds to hydrogen

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bonding [30], evidencing the chemical interaction between ZL and CHS. The FTIR spectra of the

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CHS-ECH/ZL after MB (Fig. 3b) and RR120 (Fig. 3c) uptake show a similar profile to CHS-
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ECH/ZL with a slight shift some of the bands, evidencing that various functional groups of the

CHS-ECH/ZL were contributed in the adsorption of MB and RR120.

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SEM analysis was used to examine the surface morphology of CHS-ECH/ZL, before and
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after MB and RR120 uptake. Fig. 4a-c shows the SEM micrographs for CHS-ECH/ZL before
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and after uptake of MB and RR120, respectively. In Fig. 4a, the surface morphology of CHS-

ECH/ZL appears unsmooth and rough with existence of porosity and crevices. After adsorption
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of MB (Fig. 4b) and RR120 (Fig. 4c) onto the CHS-ECH/ZL surface, the morphology of CHS-

ECH/ZL appears more compact with disappearance of porosity, in line with the MB and RR120

uptake onto the CHS-ECH/ZL surface.

3.2 Adsorption study

3.2.1. Effect of CHS-ECH/ZL dosage

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The impact of CHS-ECH/ZL dosage on MB and RR120 removal (%) was examined at

various adsorbent dosage (0.02-0.5) g; whereas, the others key factors including dye

concentration, dye solution, temperature, shaking speed, and time were stayed constant at 100

mg/L, 100 mL, 303K, and 110 strokes/min, and 180 min, respectively. As depicted in Fig. 5 the

MB and RR120 removal (%) raises remarkably from 3.3 % to 88.1 % and 7.8 % to 90.5 %,

respectively, with the increase in the quantity of the adsorbent dosage from 0.02 g to 0.2 g. The

highest removal of MB (90%) and RR120 (88%) dyes was obtained at 0.2 g, which can be

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attributed to the increase number of active adsorption sites and/or higher surface area. An

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additional increase in the CHS-ECH/AC dosage (greater than 0.2 g) did not give significant

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enhancement in the removal efficiency of the MB and RR120. Thus, 0.2 g was adopted to be an
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optimum adsorbent dosage for further investigations.

3.2.2. Effect of solution pH

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The impact of pH solution on MB and RR120 removal (%) was examined at various
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levels of solution pH (4-10) as shown in Fig. 6a. The others key factors including adsorbent
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dosage, dye concentration, dye solution, temperature, shaking speed, and time were stayed

constant at 0.2g, 100 mg/L, 100 mL, 303K, and 110 strokes/min, and 60 min, respectively. As
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depicted in Fig. 6a, the highest adsorption capacity of MB (31.3 mg/g) was achieved at solution

pH 9; whereas, the highest adsorption capacity of RR120 (40.6 mg/g) was achieved at solution

pH 6. The pHpzc of the CHS-ECH/ZL was found to be 8 as appeared in Fig. 6b. This result

reveals that the CHS-ECH/ZL surface can be acquired positive charge at pH < pHpzc and negative

charge at pH > pHpzc [45]. Accordingly, the surface of CHS-ECH/ZL can be changed into

negative charge at solution pH 9 and positive charge at solution pH 6, indicating the capability of

CHS-ECH/ZL on the adsorption of organic dyes containing cation/anion groups such as MB and

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RR120. As a result, intense electrostatic attractions can be occurred between surface functional

groups positively/negatively charged of CHS-ECH/ZL with cation/anion group of the MB and

RR120 as seen in Eq. 3 and Eq. 4, respectively as follow:

CHS − ECH/ZL− + MB+ ⟷ CHS − ECH/ZL− … … +MB (3)

CHS − ECH/ZL+ + RR120− ⟷ CHS − ECH/ZL+ … … −RR120 (4)

Thus, solution pH 9 and solution pH 6 were adopted to be optimum solution pH for MB and

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RR120 respectively for further dyes removal investigations.

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3.2.3 Effect of temperature

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The effect of temperature on the adsorption of MB and RR120 molecules onto surface of
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CHS-ECH/ZL at different temperatures (303, 313, and 323 K) were explored. The other
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parameters like CHS-ECH/ZL dose = 0.2g, dye concertation 100 mg/L, and dye solution =100
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mL were kept constant during this study for MB and RR120 dyes adsorption. Meanwhile, the

solution pH was adjusted at 9 and 6 for MB and RR120 dyes, respectively. The curves of
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adsorption capacities of CHS-ECH/ZL, qt (mg⁄g) against time (min) at different temperatures for
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MB and RR120 are exhibited in Fig. 7a and Fig. 7b, respectively. It was noticed from Fig. 7a

that the adsorption capacity of CHS-ECH/ZL towards MB molecules increased from 35.7 to 44.2

mg/g by increasing temperature from 303 to 323 K. This result indicates that the MB uptake on

CHS-ECH/ZL in an endothermic in nature [44]. The increasing in adsorption capacity of CHS-

ECH/ZL at high temperature can be attributed to the effect of temperature on the internal

structure of the CHS-ECH/ZL, thus facilitation the diffusion of MB molecules in the CHS-

ECH/ZL’s interspaces structure [46]. In Fig. 7b, the adsorption capacity of CHS-ECH/ZL

towards RR120 molecules decreased from 45.2 5 to 42.2 mg/g by increasing temperature from

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303 K to 323 K, suggesting the RR120 adsorption on CHS-ECH/ZL is an exothermic in nature.

Therefore, the solution temperature 303 K and 323 K were fixed for adsorption study of RR120

and MB dyes respectively.

3.2.4 Effect of initial dye concentration and content time

The effect of contact time on the adsorption of MB and RR120 molecules onto surface of

CHS-ECH/ZL at different initial concentrations (30, 50, 100, 200, 300, and 400 mg/L) were

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explored. The curves of adsorption capacities of CHS-ECH/ZL, qt (mg⁄g) against time (min) at

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different initial concentrations for MB and RR120 are exhibited in Fig. 8a and Fig. 8b,

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respectively. It was noticed from Fig. 8a and Fig. 8b that the adsorption capacity of CHS-

ECH/ZL towards MB and RR120 molecules increased from 14.2 to 119.6 mg/g and 13.5 to
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149.1 mg/g by increasing concentration of MB and RR120 from 30 to 400 mg/L, respectively.
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The effect relates to the higher concentration gradient that increases diffusion of dye molecules

in the internal pores of adsorbent and moving of dye molecules to active adsorption sites [47].
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3.3 Adsorption kinetics

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For better understanding on the adsorption behavior and mechanism of MB and RR120
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on the CHS-ECH/ZL surface. The two common kinetic models including pseudo-first-order

(PFO) and pseudo-second-order (PSO) were employed to evaluate the kinetics of the adsorption

of MB and RR120 on CHS-ECH/ZL surface [48, 49]. The non-linear formulas of PFO and PSO

kinetic models are presented respectively by Eq. 5 and Eq. 6 as follows:

k t
q  q (1  exp 1 )
t e (5)

qe2 k 2t
qt 
1  qe k2t
(6)

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where, qt (mg/g) and qe (mg/g) represent the amount of MB and RR120 uptake by CHS-ECH/ZL

at time (t), and at equilibrium, respectively. k1 (1/min), and k2 (g/mg min) are PFO and PSO rate

constants, respectively. The values of kinetic parameters of MB and RR120 dyes uptake on

CHS-ECH/ZL surface are summarized in Table 2. As illustrated in Table 2, greater values of R2

were achieved for PFO and PSO models of MB and RR120 dyes. Besides, the calculated qe

values for both PFO and PSO models of MB and RR120 is more in agreement with the

experimented qe values. Thus, the MB and RR120 dyes uptake on the CHS-ECH/ZL can be

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better defined by both physisorption and chemisorption [50].

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3.4 Adsorption isotherms

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Adsorption isotherm is an indispensable tool for describing the relationship between dye
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molecules and CHS-ECH/ZL composite. The most widely applied isotherms (Langmuir,
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Freundlich, and Temkin) are utilized to calculate the maximum adsorption capacity of CHS-

ECH/ZL, analyze the equilibrium adsorption data, and design of adsorption systems. The non-
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linear formulas of equilibrium isotherms including Langmuir [51], Freundlich [52], and Temkin
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[53] are presented respectively by Eqs. (7-9), as follows:

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qmax K aCe
qe  (7)
1  K a Ce

q e  K f Ce
1/ n
(8)
𝑅𝑇
𝑞𝑒 = ln(𝐾𝑇 𝐶𝑒 ) (9)
𝑏𝑇

Where Ce (mg/L) is the concentration of dye in solution at equilibrium, qmax (mg/g) indicates the

monolayer adsorption capacity of the CHS-ECH/ZL, and qe (mg/g) is the equilibrium adsorption

capacity. Ka (L/mg), Kf (mg/g) (L/mg)1/n, and KT (L/mg) are Langmuir, Freundlich, and Temkin

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constants, respectively. R (8.314J/molK), T (K), bT (J/mol), and n represent the gas constant,

temperature, heat of adsorption, and adsorption intensity, respectively.

The plots of the non-linear isotherms for MB and RR120 are presented in Fig. 9a and Fig. 9b,

while the values of isotherms parameters for MB and RR120 are given in Table 3. It can be

concluded from the R2 values for isotherm models (Table 3) that the adsorption of MB and

RR120 onto CHS-ECH/ZL surface is better described by Freundlich model, indicating the

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multilayer of the dye molecules covering the surfaces of CHS-ECH/ZL [54]. The qmax of MB and

RR120 on the CHS-ECH/ZL surface was determined to be 156.1 mg/g and 284.2 mg/g. The qmax

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of CHS-ECH/ZL for MB and RR120 is compared with others adsorption capacities of CHS

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composites utilized for adsorption of MB and RR120 as shown in Table 4. It can be deduced
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from Table 4 that the CHS-ECH/ZL is a promising zwitterion adsorbent for removal of cationic
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and anionic dyes from aquatic media.

3.5. Adsorption mechanism of MB and RR120

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Adsorption mechanism of MB and RR120 onto CHS-ECH/ZL surface was drawn (Fig.
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10) based on the available functional groups including –NH2, -OH, ≡Si-OH, and =Al-OH on the
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surface of CHS-ECH/ZL. Initially, the highest removal of MB was occurred in basic

environment (solution pH 9); whereas, the highest removal of RR120 was occurred in acidic

environment (solution pH 6), indicating the CHS-ECH/ZL was a zwitterion adsorbent. This

negative charge of the CHS-ECH/ZL is resulted from substitution some ions of Si4+ by Al3+ ions

in the tectosilicate framework of ZL, in addition to negative charges (-O¯) of CHS [63]. Thus,

electrostatic attractions can be generated between the negatively charged CHS-ECH/ZL surface

and positive groups of MB. This positive charge of the CHS-ECH/ZL is resulted from cationic

amino groups (NH3+) of CHS and positive charges (≡Si-OH2+) of ZL. Thus, electrostatic

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attractions can be generated between the positively charged CHS-ECH/ZL surface and negative

sulfonate groups (-SO3-) of RR120. Another significant factor of interaction is a hydrogen

bonding between free hydrogen of the CHS-ECH/ZL with oxygen and nitrogen in MB and

RR120 structure. In the same context, Yoshida H-bonding interaction can also be formed

between hydrogen of hydroxyl groups and aromatic rings of MB and RR120 [64]. Lastly, n-𝜋

interaction occurs between electron donating groups of oxygen and nitrogen on CHS-ECH/ZL

surface and π-system (electron acceptor) in the aromatic rings of MB and RR120 [44].

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4. Conclusion

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CHS-ECH/ZL composite was successfully prepared and applied as a zwitterion

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composite adsorbent for the removal of cationic (MB), and anionic (RR120) dyes from aqueous
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solutions. The results illustrated that the highest removal for MB and RR120 was observed at the

following conditions: adsorbent dosage 0.2 g; solution pH 9 for MB, and solution pH 6 for
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RR120; and temperature 323 K for MB and 303 K for RR120. The experimental data of the
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adsorption isotherms clarified that the MB and RR120 adsorption was multilayer on the surface

of CHS-ECH/ZL. The remarkable absorption capacities of CHS-ECH/ZL towards MB (156.1

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mg/g) and RR120 (284.2 mg/g) were achieved. The mechanism of MB and RR120 adsorption
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onto the CHS-ECH/ZL included chemical adsorption, namely, electrostatic interactions,

hydrogen bonding, and Yoshida H-bonding in addition to n-π interactions. This study

demonstrates that CHS-ECH/ZL offers multifunctional adsorptive performances towards

removal of the cationic and anionic dyes from aqueous environment.

Acknowledgements

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The authors would like to thank Ministry of Education, Malaysia for supporting this

research project under fundamental research grant scheme (600-IRMI/FRGS/5/3 (340/2019);

FRGS/1/2019/STG01/UiTM/02/3).

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Tables

Table 1: The textural properties of CHS-ECH/ZL

Property Value
BET surface area (m2/g) 1.42
Total pore volume (cm3/g) 0.011
Mean pore diameter (nm) 32.0
Vm (cm3 /g) 0.32

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Table 2: PFO and PSO kinetic parameters for the adsorption MB dye and RR120 dye on
CHS-ECH/ZL.

MB qe exp. -p PFO
2
PSO
k2×10-2 R2
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Concentration (mg/gm) qe cal k1 R qe cal
(mg/L) (mg/gm) (1/min) (mg/gm) (g/mg min)
30 14.2 13.9 0.181 0.98 14.3 2.269 0.99
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50 23.2 22.7 0.130 0.98 23.6 0.956 0.99

100 35.7 35.1 0.064 0.98 37.0 0.295 0.99
200 70.9 70.0 0.030 0.98 72.8 0.060 0,99
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300 102.3 95.7 0.024 0.97 105.9 0.031 0.99

400 119.6 112.9 0.025 0.94 123.7 0.029 0.98
RR120 qe exp. PFO PSO
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Concentration (mg/gm) qe cal k1 R2 qe cal k2 x 10-2 R2

(mg/L) (mg/gm) (1/min) (mg/gm) (gm/mg
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min)
30 13.5 12.9 0.237 0.97 13.3 3.160 0.99
50 22.4 22.0 0.025 0.98 23.9 0.153 0.99
100 46.4 45.8 0.016 0.99 51.6 0.041 0.99
200 76.8 71.6 0.017 0.96 81.1 0.026 0.99
300 115.6 112.3 0.014 0.99 119.0 0.013 0.99
400 149.1 140.5 0.015 0.98 154.1 0.012 0.99

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Table 3: Parameters of the Langmuir, Freundlich and Temkin isotherm models for the
adsorption of MB at 323 K, and RR120 at 303 K by CHS-ECH/ZL.

Adsorption isotherm Parameter MB RR120

Langmuir qm (mg/gm) 165.1 284.2
Ka (L/mg) 0.012 0.010
R2 0.96 0.95

Freundlich Kf (mg/gm) (L/mg)1/n 8.16 7.15

N 1.9 1.5
R2 0.99 0.98

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Temkin KT (L/mg) 0.8 0.9

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bT (J/mol) 103.8 73.9
R2 0.92 0.90

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Table 4: Comparative of adsorption capacities for MB and RR120 dyes by different CHS
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composites

CHS composites Dye qmax References

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(mg/g)
CHS-ECH/ZL composite MB 156.1 This study
CHS-ECH/ZL composite RR120 284.2 This study
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Graphene oxide-chitosan @Cu3(btc)2 composite MB  357.14 [20]

Cross-linked succinyl chitosan MB 289.02 [ 55]
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Porous 3D network rectorite/chitosan MB 162.6 [56]

Chitosan/nano-lignin based composite MB 74.07  [57]
Magadiite-chitosan composite MB 45.25  [58]
H2SO4 crosslinked magnetic chitosan MB 20.408  [59]
nanocomposite
Chitosan-iron(III) crosslinked RR120 361.9 [60]
Cross-linked chitosan-ECH/TiO2 nanocomposite RR120 210 [44]
Biofilm of cross-linked chitosan-ethylene glycol RR120 165.3 [61]
diglycidyl ether
Schiff’s base-cross-linked chitosan composite RR120 103 [4]
Chitosan/zeolite composite RR120 19.14 [62]

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Figures Caption

Fig. 1 Synthesis steps of CHS-ECH/ZL.

Fig. 2 XRD patterns of (a) ZL and (b) CHS-ECH/ZL.

Fig. 3 FTIR spectra of (a) CHS-ECH/ZL and CHS-ECH/ZL after adsorption of

(a) MB dye and (c) RR120 dye.

Fig. 4 SEM images of (a) CHS-ECH/ZL and CHS-ECH/ZL after adsorption of

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(a) MB dye and (c) RR120 dye.

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Fig. 5 Effect of adsorbent dosage on MB and RR120 removal, [Dye]o = 100
mg/L, V = 100 mL, unadjusted pH, T = 303 K, shaking speed = 110 rpm
and contact time = 180 min.
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Fig. 6 (a) Effect of solution pH on MB and RR120 removal, [Dye]o = 100 mg/L,
V = 100 mL, adsorbent dose = 0.2 g, T = 303 K, shaking speed = 110 rpm
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and contact time = 180 min, (b) pHpzc of CHS-ECH/ZL.

Fig. 7 Effect of temperature on adsorption of (a) MB, and (b) RR120 at different
temperatures (303, 313, and 323 K) by CHS-ECH/ZL.
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Fig. 8 (a) Effect of the contact time on adsorption of (a) MB dye at 323 K, and
(b) RR120 dye at 303 K, at different initial dye concentrations by CHS-
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ECH/ZL (dosage 0.2 g, solution pH 9 for MB dye and solution pH 6 for

RR120, agitation speed 110 strokes and volume of solution 100 mL)
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Fig. 9 Adsorption isotherms of (a) MB at 323 K, and (b) RR120 at 303 K by

CHS-ECH/ZL (dosage 0.2 g, solution pH 9 for MB dye, and solution pH 6
for RR120 dye, agitation speed 110 strokes and volume of solution 100
mL).

Fig. 10 Illustration of the possible interaction between CHS-ECH/ZL with MB ,

and RR120 including electrostatic attraction, H-bonding interaction,
Yoshida H-bonding, and n-𝜋 interactions.

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Declaration of competing interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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