Journal Pre-proofs

Tunable Schiff’s base-cross-linked chitosan composite for the removal of re-

active red 120 dye: Adsorption and mechanism study

Ali H. Jawad, Nur Shazwani Abdul Mubarak, Ahmed Saud Abdulhameed

PII: S0141-8130(19)36472-4
DOI: https://doi.org/10.1016/j.ijbiomac.2019.10.014
Reference: BIOMAC 13394

To appear in: International Journal of Biological Macromole-

cules

Received Date: 14 August 2019

Revised Date: 29 September 2019
Accepted Date: 1 October 2019

Please cite this article as: A.H. Jawad, N. Shazwani Abdul Mubarak, A. Saud Abdulhameed, Tunable Schiff’s
base-cross-linked chitosan composite for the removal of reactive red 120 dye: Adsorption and mechanism study,
International Journal of Biological Macromolecules (2019), doi: https://doi.org/10.1016/j.ijbiomac.2019.10.014

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 Tunable Schiff’s base-cross-linked chitosan composite for the removal of reactive red 120

dye: Adsorption and mechanism study

Ali H. Jawada,*,ali288@uitm.edu.my,ahjm72@gmail.com, Nur Shazwani Abdul Mubaraka, Ahmed Saud

Abdulhameedb

aSchool
of Chemistry and Environment, Faculty of Applied Sciences, Universiti Teknologi
MARA, 40450 Shah Alam, Selangor, MALAYSIA

bChemistry Department, College of Science, University of Anbar, Ramadi, IRAQ

*Corresponding author:

Abstract

In this study, tunable Schiff’s base-cross-linked chitosan-glutaraldehyde (CS-GLA) was

modified and applied to remove reactive red 120 (RR120) dye from an aqueous solution.

Different ratios of TiO2 nanoparticles, such as 25% TiO2 nanoparticles (CS-GLA/TNC-25) and

50% TiO2 nanoparticles (CS-GLA/TNC-50), were loaded into the CS-GLA’s molecular

structure. The adsorptive properties of CS-GLA, CS-GLA/TNC-25, and CS-GLA/TNC-50 for

the RR120 dye in the aqueous solution were evaluated. CS-GLA/TNC-25 exhibited the best

adsorptive property possibly because of the perfect balancing between the surface area and

1
available amine (–NH2) groups in the composite formulation. The impact of adsorption key

parameters, such as adsorbent dosage (0.01–1.2 g/mL), RR120 dye concentration (30–400

mg/L), solution pH (3–12), and contact time (0–400 min) were explored by batch adsorption

mode. The adsorption was well described by the Freundlich model and pseudo-second order

kinetic model. The adsorption capacity of CS-GLA/TNC-25 for RR120 dye was 103.1 mg/g at

30 °C. The adsorption mechanism of RR120 on the CS-GLA/TNC-25 surface can be assigned to

various interactions, such as electrostatic attraction, n–π stacking, and H-bonding. Results

indicate the potential application of CS-GLA/TNC-25 as environment-friendly biosorbent for

removing acid and/or textile dyes, such as RR120, from aqueous environments.

Keywords: Chitosan; TiO2 nanoparticles; Glutaraldehyde; Schiff’s base; Reactive red 120 dye;

Adsorption

1. Introduction

Reactive azo dyes are widely used in textile industries and represent a large proportion of

dyes discharged into the environment [1]. These azo dyes contain one or more azo (–N=N–)

groups with heterocyclic and aromatic rings in addition to some functional groups, such as

sulfonates and chloride [2]. The azo groups within the structures of these dyes have low

biodegradability and thus present many risks [3]. Therefore, removing these dyes before

releasing them into the environment is necessary. Several methods, such as adsorption [4],
2
photocatalysis [5], advanced oxidation processes [6], and coagulation [7], have been applied to

remove these dyes prior to discharge into water. However, several disadvantages, such as

consumption of energy and chemicals, complicated operation, high cost, and generation of toxic

materials [8-10], limit the application of these techniques in wastewater treatment. Adsorption is

considered one of the most efficient methods for removing contaminants because of its easy

operation, nongeneration of toxic materials, operational feasibility, low cost, and high efficiency

[11,12].

Chitosan (CS) is a linear biopolymer and considered the second most abundant polymer

in nature produced from marine organisms, such as shrimp and crabs [13]. CS exhibits many

desirable properties, such as nontoxicity, biodegradability, antimicrobial effect, and

biocompatibility [14]. These properties enable CS its use in many fields especially in wastewater

treatment and medical applications [15, 16]. The availability of the reactive amino (–NH2) and

hydroxyl (–OH) groups on the molecular structure of CS make CS a benchmark biosorbent in

wastewater treatment technologies [17]. However, the application of unmodified CS in

wastewater treatment technology is still limited due to its high solubility in acidic environment,

leachability, and swelling in aqueous medium [18]. In fact, many modification methods have

been applied to modify CS either by cross-linking reaction or by mixing with nanomaterial to

improve the physicochemical, structural, porosity, and adsorptive property of CS [19].

Glutaraldehyde (GLA; 1,5-pentanodial) is one of the most common cross-linking agents

that bind preferentially to the amino (–NH2) group C-2 position of CS with active dialdehyde

groups. Irreversible imine bond forms during Schiff’s base formation. This cross-linking reaction

can offer chemically stable and mechanically resistant CS derivatives. However, the cross-

3
linking reaction with GLA decreases the availability of free amino (–NH2) group as active

adsorption sites [20]. Recently, CS-based Schiff base compounds have been widely synthesized

and utilized in several applications, such as drug delivery [21], dye degradation [22], removal of

metals [23], and as an antimicrobial agent [24]. In fact, not only the chemical stability and

mechanical resistance but also the surface properties and porosity of CS derivatives are

important. The incorporation of nanomaterials, such as titanium dioxide (TiO2) nanoparticles, in

the molecular structure of CS is responsible for enhancing the surface area, porosity, and

adsorption capacity of CS [25]. Furthermore, TiO2 nanoparticles introduce two hydroxyl groups

on adsorbent surfaces involved in the adsorption of acid dyes [15, 26].

TiO2 has many preferable properties, such as high surface area, relatively low cost, high

chemical stability in acidic and alkaline media, nontoxicity, and insolubility in water [27].

Therefore, the composite biomaterials of CS-TiO2 have been widely utilized as promising

multifunctional materials in various applications, such as wastewater treatment [28], food

packaging [29], biosensors [30], and antimicrobial agents [31]. These promising applications

inspire us to develop tunable hybrid Schiff’s base CS/TiO2 nanoparticles as biosorbents for

textile dyes from aqueous environments. A tunable Schiff’s base-cross-linked chitosan-

glutaraldehyde/TiO2 nanoparticles (CS-GLA/TNC) were synthesized. The process was

conducted by loading different ratios of TiO2 nanoparticles into the molecular structure of CS-

GLA for the production of a tenable composite biopolymer exhibiting perfect balancing between

surface area property and amino (–NH2) group content. We also identified the effectiveness of

CS-GLA/TNC to remove reactive red 120 (RR120) dye as a model polyaromatic reactive azo

dye from an aqueous solution. These adsorbents were optimized for selection of the best

4
adsorbent for RR120 dye removal. A comprehensive adsorption and mechanism study of RR120

on the surface of CS-GLA/TNC was adequately discussed.

2. Materials and methods

2.1 Materials

CS (deacetylation 68%; medium molecular weight), TiO2 Degussa P-25, and

glutaraldehyde (GLA; 50% solution) were obtained from Sigma-Aldrich. Reactive red 120 dye

(RR120; C44H24Cl2N14Na6O20S6, MW: 1469.34 g/mol, and λmax=534 nm) was supplied from

ACROS, Organics. Hydrochloric acid, sodium hydroxide, and acetic acid were purchased from

R&M Chemicals. All experiments in this research were performed using ultrapure water.

2.2 Synthesis of chitosan-glutaraldehyde/TiO2 nanocomposite (CS-GLA/TNC)

The cross-linked chitosan-glutaraldehyde (CS-GLA) was synthesized by dissolving 1 g of

CS flakes in acetic acid (50 mL, 5% v/v). The solution was left for 24 h at room temperature

with vigorous stirring for the dissolution of the CS flakes. The resultant solution was injected

into 1000 mL of sodium hydroxide (0.5 M) by a syringe needle (10 mL). The CS beads formed

instantaneously. The fresh beads of CS were washed many times with distilled water for the

removal of excess sodium hydroxide solution. The cross-linking step was carried out by adding

1% GLA (100 mL) to the CS beads with mild stirring in water bath at 40 °C for 2 h. Then, the

CS-GLA beads were washed many times with distilled water and air-dried. A series of CS-

GLA/TNCs was synthesized by loading different ratios of TiO2 nanoparticles with the CS flakes

(75% CS:25% TiO2 nanoparticles) and (50% CS:50% TiO2 nanoparticles) and then dissolved in

acetic acid (50 mL, 5% v/v). The composite materials were cross-linked with GLA through the

5
same cross-linking procedure above. Then, the cross-linked CS-GLA/TNC with constant loading

ratio of 75% CS:25% TiO2 was labeled as CS-GLA/TNC-25, whereas that with constant loading

ratio of 50% CS:50% TiO2 was labeled as CS-GLA/TNC-50. The particle size of the powder

form of all applied materials was fixed to uniform particle size ≤250 μm for all adsorption

experiments. The synthesis steps of CS-GLA/TNC are presented in Fig. 1.

2.3 Adsorbent characterization

The surface areas and pore structures of the samples were determined by N2

adsorption/desorption isotherms at temperature of 77 K with a Micromeritics ASAP 2020

analyzer. Elemental analysis (CHN; Flash 2000, Organic Elemental Analyzer, Thermo-scientific,

Netherlands) was performed to determine the elemental composition of the adsorbents. The

crystalline nature of the samples was analyzed with an X-ray diffractometer (X’Pert PRO,

PAnalytical). A scanning electron microscope (Zeiss Supra 40 VP, Germany) was used to

analyze the surface morphology of samples before and after RR120 adsorption. The amino (–

NH2) group content in the synthesized martials was determined by pH-potentiometric titration

according to the method reported by Vieira and Beppu [32]. The pH at the point of zero charge

(pHpzc) was calculated according to the published method [33]. A Fourier transform infrared

spectrometer (Perkin-Elmer, Spectrum RX I) was employed to identify the functional groups of

the adsorbents before and after RR120 adsorption.

2.4 Batch adsorption studies

6
 The RR120 dye adsorption on the adsorbents (CS-GLA, CS-GLA/TNC-25, and CS-

GLA/TNC-50) was investigated in batch adsorption mode. The experiments were performed in

250 mL Erlenmeyer flasks containing 100 mL of RR120 dye solution with different initial

RR120 dye concentrations (30–400 mg/L). The adsorbent at different dosages (0.02–0.2 g) was

added to 100 mL of RR120 dye solutions with different levels of pH (3–12) and agitated at a

fixed shaking speed of 90 strokes/min at 303 K by using an isothermal water bath shaker

(WNB7-45, Memmert, Germany). Then, a syringe filter (0.20 µm) was used to separate the

adsorbents. The initial and final concentrations of RR120 dye were calculated using a UV–Vis

spectrophotometer (HACH DR 2800) at the maximum wavelength of 534 nm. The dye removal

of RR120 (DR%) and adsorbed amount of RR120 dye at equilibrium, 𝑞𝑒 (mg/g), were

determined using Eqs. (1) and (2), respectively.

(𝐶𝑜 ― 𝐶𝑒)
𝐷𝑅 % = 𝐶𝑜 × 100 (1)

(𝐶𝑜 ― 𝐶𝑒)𝑉
𝑞𝑒 = 𝑊
(2)

where Co (mg/L) is the initial concentration of the RR120 dye, and Ce (mg/L) is the RR120 dye

concentration at equilibrium. V is the volume of dye solution (L), and W is the amount of

adsorbent (g).

3. Results and Discussion

3.1 Characterization

3.1.1 Physicochemical properties

7
 The BET surface areas and mean pore diameters of CS-GLA, CS-GLA/TNC-25, and CS-

GLA/TNC-50 are recorded in Table 1. BET surface area analysis shows that CS-GLA had a

lower surface area (0.37 m²/g) than CS-GLA/TNC-25 (2.04 m²/g) and CS-GLA/TNC-50 (6.4

m²/g). These results indicate clearly that loading several TiO2 nanoparticles into the molecular

structure of CS-GLA enhanced the surface area of the composite materials. In other words, the

surface area of CS-GLA/TNC-25 and CS-GLA/TNC-50 increased approximately ~6 times and

~17 times by loading 25% TiO2 and 50% TiO2 nanoparticles, respectively, into the molecular

structure of CS-GLA. The pore diameter measurements (Table 1) indicate that CS-GLA, CS-

GLA/TNC-25, and CS-GLA/TNC-50 were mesoporous materials according to the IUPAC

classification (USA) [34].

Potentiometric titration analysis was carried out to calculate the content (%) of the amino

(–NH2) group in the molecular structures of CS-GLA, CS-GLA/TNC-25, and CS-GLA/TNC-50.

The results of potentiometric titrations are presented in Table 1, indicating the decreased amino

(–NH2) group contents of CS-GLA (38.64%), CS-GLA/TNC-25 (22.54%), and CS-GLA/TNC-

50 (14.49%). These results reveal the decreasing contents (%) of the amino (–NH2) group with

the increasing ratio of TiO2 nanoparticles. In general, TiO2 incorporation in the matrix of CS

decreases amino (–NH2) content due to the interaction between the Lewis acidic sites of titanium

dioxide and basic sites of the amino groups in CS [28]. The cross-linking reaction with GLA

leads also to decrease the amino (–NH2) content of CS caused by the GLA reacting with the

amino groups of CS [35]. This obvious gradual reduction in the amino (–NH2) group content

with gradual increment in TiO2 nanoparticles loading into the molecular structure of CS-GLA

can be attributed to the physical mixing of 75% and 50% CS flakes with 25% and 50% of TiO2

nanoparticle powder during the preparation of composite CS-GLA/TNC. Another reason is the
8
blocking of the amino (–NH2) group of CS by the aldehyde group of the cross-linker agent

(GLA) by chemical cross-linking reaction [14]. The elemental analysis (CHN) was performed to

determine the elemental composition of CS-GLA, CS-GLA/TNC-25, and CS-GLA/TNC-50 as

recorded in Table 1.

3.1.2 XRD analysis

XRD was performed to determine the amorphous and crystalline nature of CS-GLA

before and after loading TiO2 nanoparticles into its molecular structure. The XRD patterns of

CS-GLA, CS-GLA/TNC-25, and CS-GLA/TNC-50 are presented in Fig. 2. As shown in Fig. 2a,

a single broad peak at 2θ=20° was observed, indicating the amorphous structure of CS-GLA. The

XRD pattern of the CS-GLA/TNC-25 is given in Fig. 2b. Numerous sharp and distinguished

peaks were observed at 2θ=25°, 38°, 48°, 54°, 62°, 68°, 74°, and 82°. The presence of these

peaks indicates that the CS-GLA/TNC-25 composite had high crystallinity, which was

emphasized during the incorporation of TiO2 nanoparticles into the molecular structure of CS-

GLA. The CS-GLA/TNC-25 crystallinity can be attributed to the intermolecular and

intramolecular hydrogen bonding [36]. The XRD pattern of CS-GLA/TNC-50 (Fig. 2c) exhibits

similar peaks for CS-GLA/TNC-50 with enhancing in intensity of some peaks due to loading of

the TiO2 nanoparticles.

3.1.3 FTIR analysis

9
 FTIR analysis was performed to determine the functional groups on the surface of

adsorbents, prove the interaction between the TiO2 nanoparticles and CS, and show changes in

the functional groups on the CS-GLA/TNC-25 surface after RR120 dye adsorption. The FTIR

spectra of CS-GLA, CS-GLA/TNC-25, and CS-GLA/TNC-25 after RR120 dye adsorption are

presented in Fig. 3. The FTIR spectrum of CS-GLA displays characteristic peaks at ~3400 and

1340 cm−1 for stretching vibration of the O–H and N–H and C–N bonds, respectively [19]. The

peak at ~1660 cm−1 indicates a stretching vibration of the C=N bond formed by the cross-linking

reaction between the carbonyl groups of GLA and amino groups of CS [37]. The peaks at ~1150

and ~1040 cm−1 corresponded to the stretching vibrations of C–O–C and C–O bonds [38]. In Fig.

3b, the broad band at ~500–700 cm−1 was assigned to the bending vibration of the Ti–O–Ti

bonds, whereas the peaks at 2851 and 3429 cm−1 corresponded to the O–H of the TiO2 surface

[28]. These peaks indicate the possible interaction between the TiO2 and functional groups (–NH2

and –OH) of CS. The FTIR spectrum after RR120 dye adsorption (Fig. 3c) showed appearance

of new peak at~1450 cm−1 and reducing in intensity of some bands. This phenomenon can be

attributed to the polyaromatic ring (C=C) of RR120 molecules adsorbed on the CS-GLA/TNC-

25 surface.

3.1.4 SEM analysis

SEM analysis was performed to observe the surface morphology of adsorbents, loading

of TiO2 nanoparticles into the molecular structure of CS, and CS-GLA/TNC-25 surface after

RR120 dye adsorption. Figs. 4a, 4b, 4c, and 4d show the SEM images of CS-GLA, CS-

GLA/TNC-25, CS-GLA/TNC-50, and CS-GLA/TNC-25 after RR120 dye adsorption,

respectively. As shown in Fig. 4a, the surface morphology of CS-GLA was irregular, rough, and

10
heterogonous. The CS-GLA surface after the loading of TiO2 nanoparticles was altered and

showed cavities and pores. TiO2 nanoparticles were equally distributed, as shown in Fig. 4b.

Many cavities and pores were observed after the loading of TiO2 nanoparticles into the

polymeric structure of CS-GLA/TNC-25, as shown in Fig. 4c. Surface area analysis previously

showed that loading several TiO2 nanoparticles enhances surface area property. However, the

surface of CS-GLA/TNC-25 after the RR120 dye adsorption was compact, and many cavities

and pores were blocked by the adsorbed RR120 dye molecules adsorbed on the CS-GLA/TNC-

25 surface (Fig. 4d).

3.2 Batch adsorption study

3.2.1 Effect of TiO2 loading and adsorbent dose
The influence of loading TiO2 nanoparticles into the molecular structure of CS-GLA on

the adsorptive properties of composite material was investigated. The adsorbent doses of the

three types of adsorbents for the removal of RR120 dye were tested. Fig. 5 shows that CS-

GLA/TNC-25 adsorbent had the highest removal rate (99.64%) at 0.3 g, followed by CS-GLA

and CS-GLA/TNC-50 with 50.4% and 43.36%, respectively. However, CS-GLA had the highest

recorded amino (–NH2) group content (Table 1), and CS-GLA/TNC-50 had the highest recorded

surface area (Table 1). Meanwhile, CS-GLA/TNC-25 with lower amino (–NH2) group content

than CS-GLA and lower surface area than CS-GLA/TNC-50 exhibited the best adsorptive

property toward RR120 dye. This observation clearly shows that high amino (–NH2) group

content and high surface area of adsorbent are important factors. In addition, the tuning process

and perfect balancing between the amino (–NH2) group content and surface area are significant,

as confirmed by CS-GLA/TNC-25. In fact, CS-GLA/TNC-25 with this amino (–NH2) group

11
content plays an important role in the adsorption of RR120 by electrostatic attraction between

positively charged protonated amino groups (–NH3+) on the CS-GLA/TNC surface and the

negatively charged group of the RR120 dye. Furthermore, TiO2 nanoparticles play an important

role during adsorption by enhancing the surface area of the CS-GLA/TNC composite and

introducing two hydroxyl groups on the adsorbent surface [19]. Thus, CS-GLA/TNC-25 was

considered the best tunable composite biosorbent for performing comprehensive RR120 dye

adsorption.

3.2.2 Effect of solution pH

pH is one of the important parameters that affect dye adsorption because is determines

the degree of the ionization of adsorptive molecules and surface charge of adsorbents. The effect

of initial solution pH on the adsorption capacity of RR120 dye onto the CS-GLA/TNC-25 was

identified at different levels (pHs 3–12) at the fixed values of the key parameters (adsorbent

dosage 0.3 g/100 mL, RR120 dye concentration 100 mg/L, and contact time 360 min). Fig. 6a

shows that the decrease in solution pH from 12 to 3 increased the adsorption capacity. Notably,

the highest adsorption capacity of the RR120 dye was observed at pH 3, and a slight decrease in

adsorption capacity was observed in an alkaline medium. The pHpzc value of CS-GLA/TNC-25

was 7.03, as shown in Fig. 6b. This result indicates that the CS-GLA/TNC-25 can exhibit

cationic acid characteristics and reinforces the availability of amino (–NH3+) cationic ions on

CS-GLA/TNC-25 surfaces. This result is in agreement with the potentiometric titration test. The

CS-GLA/TNC-25 surface can be converted to positive charge at pH value below the pHpzc, thus

promoting of the uptake of negatively charged species, such as the RR120 dye. Consequently, a
12
strong electrostatic attraction might have occurred between positively charged amino (–NH3+)

groups on the adsorbent surface and negatively charged sulfonate (–SO3−) groups of the RR120

dye. Thus, the dye removal efficiency was increased, as shown in Eq. (3).

R ― NH3+ + RR120 ― SO3― ⟷ R ― NH3+ ― SO3― ― RR120 (3)

Moreover, new hydroxyl groups can be introduced on the CS-GLA/TNC-25 surface by

composition CS-GLA with TiO2 nanoparticles [25, 28]. These groups on the CS-GLA/TNC-25

surface will be protonated and converted in the acidic medium to the positive oxonium ions [19].

Thus, the CS-GLA/TNC-25 surface becomes active adsorption sites for the negative sulfonate (–

SO3−) groups of the RR120 dye.

3.2.3 Effect of contact time and initial RR120 concentration

The effect of contact time and initial RR120 dye concentration on the adsorption

equilibrium was investigated. The adsorption capacity, qt (mg/g) against time at different initial

RR120 dye concentrations of 30, 50, 100, 150, 200, 250, 300, 350, and 400 mg/L is studied and

shown in Fig. 7. Other key parameters, such as adsorbent dose of 0.3 g, pH solution of 3, and

temperature of 303 K, remained constant within this study. Fig. 7 shows that the quantity of

RR120 dye molecules adsorbed on the surface of CS-GLA/TNC-25 increased from 8.6 mg/g to

97.2 mg/g with the increase of the initial RR120 dye concentrations from 30 mg/L to 400 mg/L.

This result can be attributed to the high concentration gradient, providing a driving force to move

the RR120 dye molecules toward the active adsorption sites [39].

13
3.3 Adsorption kinetics

For the identification of the mechanism of the RR120 dye adsorption onto the CS-

GLA/TNC-25 biomaterial, the kinetic models of pseudo-first-order (PFO) and pseudo-second-

order (PSO) were applied to examine the experimental results at different initial RR120 dye

concentrations. The nonlinear forms of the PFO [40] and PSO [41] models are expressed by Eqs.

(4) and (5), respectively.

𝑞𝑡 = 𝑞𝑡(1 ― 𝑒𝑥𝑝 ― 𝑘1𝑡 ) (4)

𝑞2𝑒 𝑘2𝑡
𝑞𝑡 = 1 + 𝑞2𝑘 𝑡 (5)
𝑒 2

where qe (mg/g) is the amount of the RR120 dye adsorbed by CS-GLA/TNC-25 at equilibrium,

and qt (mg/g) is the amount of RR120 dye adsorbed by CS-GLA/TNC-25 at time (t). k1 (1/min)

and k2 (g/mg min) are the rate constants of PFO and PSO, respectively. The kinetic parameters of

the PFO and PSO models are presented in Table 2. Experimental results (Table 2) revealed that

the RR120 adsorption by the CS-GLA/TNC-25 follows the PSO model due to the high

correlation coefficient (R2) values. In addition, the values of the calculated qe (qe,cal) from the

PSO model was close to the values of the experimental qe (qe,exp), suggesting that the RR120 dye

adsorption may be due to electrostatic attraction between the positively charged amino (–NH3+)

group on the adsorbent surface and negatively charged sulfonate (–SO3−) group of the RR120

dye [42]. Thus, electrostatic attraction plays an important role in RR120 dye adsorption by CS-

GLA/TNC-25.

3.4 Adsorption isotherms

14
 Adsorption isotherm was utilized to describe the interaction between the adsorbates and

the CS-GLA/TNC-25 adsorbent. Four isotherm models of Langmuir, Freundlich, and Temkin

were applied to investigate the equilibrium isotherms of adsorption and calculate the maximum

adsorption capacity and mean free energy of adsorption. The Langmuir model [43] is presented

by Eq. (6).

𝑞𝑚𝑎𝑥𝐾𝑎𝐶𝑒
𝑞𝑒 = 1 + 𝐾𝑎𝐶𝑒 (6)

where qe (mg/g), qmax (mg/g), Ce (mg/L), and Ka (L/mg) are the uptake amount of dye at

equilibrium, dye concentration at equilibrium, Langmuir maximum adsorption capacity, and

Langmuir constant, respectively. The Freundlich model [44] is given by Eq. (7).

1
𝑛
𝑞𝑒 = 𝐾𝑓𝐶𝑒 (7)

where Kf (mg/g) (L/mg)1/n and n are the Freundlich constant and adsorption intensity,

respectively. The Temkin isotherm model [45] is expressed by the following Eq. (8).

𝑅𝑇
𝑞𝑒 = 𝑏𝑇 ln
(𝐾𝑇𝐶𝑒)𝑚 (8)

where KT (L/mg), R (8.314 J/mol K), T (K), and bT (J/mol) are the Temkin constant, universal

gas constant, absolute temperature, and heat of adsorption, respectively.

The nonlinear plots of the studied isotherm models relating to Eqs. 6, 7, and 8 are

displayed in Fig. 8. The isotherm parameters of the models are presented in Table 3. According

to the correlation coefficient (R2) values given in Table 3, the Freundlich isotherm has the

highest correlation (R2=0.98), indicating that the RR120 adsorption occurred on heterogeneous

15
surface [46]. The maximum adsorption capacity of CS-GLA/TNC-25 for RR120 dye was found

to be 103.1 mg/g. The adsorption capacity of the RR120 dye by CS-GLA/TNC-25 was compared

with various adsorbents as given in Table 4. From Table 4, the CS-GLA/TNC-25 has a relatively

high adsorption capacity, indicating that it can be considered a convenient and effective

composite biosorbent for the removal of acid textile dyes, such as RR 120, from aqueous

environments.

3.5 Adsorption mechanism

The adsorption mechanism of the RR120 dye on the CS-GLA/TNC-25 surface can be

attributed to various types of interactions, as shown in Fig. 9. The electrostatic attractions (Fig.

9a) between the positively charged protonated amino (–NH3+) groups and (–OH) hydroxyl

groups occurred on the CS-GLA/TNC-25 surface with negatively charged sulfonate (SO3−)

groups of the RR120 dye. The adsorption mechanism included two types of hydrogen bonds,

namely, dipole–dipole hydrogen bonding and Yoshida H bonding. Dipole–dipole H-bonding

interactions (Fig. 9b) can occur between the hydrogen in the CS-GLA/TNC-25 surface and

atoms of O and N in the RR120 dye structure, whereas the Yoshida H bonding (Fig. 9c) can

occur between –OH in the surface of CS-GLA/TNC and aromatic ring of dye [54]. Finally, the

n–π interaction (Fig. 9d) occurred by delocalization of the lone pair electron of the oxygen atom

into the π orbital of the aromatic ring [55].

4. Conclusion

A Schiff’s base-cross-linked CS-GLA/TNC as an inorganic–organic hybrid

nanocomposite was successfully synthesized and used as an effective bioabsorbent to remove

16
RR120 dye. Notably, the perfect balancing between the amino (–NH2) group content and surface

area property is the main factor that demonstrates the adsorptive property of this composite

material rather than the individual effect of either the amino (–NH2) group content and/or surface

area of the composite adsorbent. In this regard, CS-GLA/TNC-25 exhibited the best adsorptive

property over CS-GLA and CS-GLA/TNC-50. The kinetics and isotherm model results indicate

that adsorption is affected by chemisorption and multilayer adsorption. The maximum adsorption

capacity of CS-GLA/TNC-25 obtained from the Langmuir model was 103.1 mg/g. The RR120

dye adsorption mechanism involved many interactions, such as electrostatic attraction, n–π

stacking, and H-bonding. This result indicates that CS-GLA/TNC-25 can be used as an efficient

adsorbent in the adsorption for the removal of reactive azo dyes from aqueous environments.

Acknowledgments

The authors would like to thank the Ministry of Higher Education (MOHE), Malaysia for

supporting this project under Fundamental Research Grant Scheme (FRGS):

FRGS/1/2019/STG01/UiTM/02/3, No,. Fail RMC: 600-IRMI/FRGS 5/3 (340/2019).

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Fig. 1. Synthesis steps of CS-GLA/TNC.

Fig. 2. XRD patterns of (a) CS-GLA, (b) CS-GLA/TNC-25, and (c) CS-GLA/TNC-50.

Fig. 3. FTIR spectra of (a) CS-GLA, (b) CS-GLA/TNC-25, and (c) CS-GLA/TNC-25 after
adsorption RR120 dye.

Fig. 4. SEM images of (a) CS-GLA, (b) CS-GLA/TNC-25, (c) CS-GLA/TNC-50, and (d) CS-
GLA/TNC-25 after RR120 adsorption at 5000 kx.

Fig. 5. Effect of adsorbent dose on the removal of RR120 dye.

Fig. 6. (a) Effect of solution pH on the adsorption of RR120 dye, and (b) pHpzc of CS-
GLA/TNC-25.

Fig. 7. Effect of contact time and initial concentration on the adsorption of RR120 dye by CS-
GLA/TNC-25 (pH = 3, adsorbent dose = 0.3 g, temperature = 303 K, agitation speed = 90
strokes and volume of solution = 100 mL).

Fig. 8. Isotherm models plots of Langmuir, Freundlich, and Tempkin for the adsorption of
RR120 dye on CS-GLA/TNC-25 at 303 K (pH = 3, adsorbent dose = 0.3 g, agitation speed = 90
strokes and volume of solution = 100 mL).

Fig. 9. Illustration of the possible interaction between CS-GLA/TNC-25 and RR120 dye: (a)
electrostatic attraction, (b) dipole–dipole hydrogen bonding interactions, (c) Yoshida H-bonding,
and (d) n-π stacking interactions.

23
Table 1. The physicochemical properties of the CS-GLA, CS-GLA/TNC-25, and CS-
GLA/TNC-50.

Analysis CS-GLA CS-GLA/TNC-25 CS-GLA/TNC-50

Surface properties

BET surface area (m²/g) 0.37 2.04 6.4

Mean pore diameter (nm) 11.16 24.4 25.76

pH-Potentiometric titration 38.64 22.54 14.49

-NH2 (%)

Elemental analysis (wt. %)

C 41.78 30.50 22.63

H 6.44 4.71 3.58

N 5.78 4.67 3.24

Table 2. PFO and PSO kinetic parameters for RR120 dye adsorption on CS-GLA/TNC-25

Co qe cal (mg/g) PFO PSO

(mg/L)
qe cal k1 R2 qe cal k2 R2
(mg/g) (1/min) (mg/g) (g/mg
min)

30 8.5 8.4 1.5 0.99 8.5 1.15 0.99

24
50 15.9 15.3 0.55 0.98 15.9 0.07 0.99

100 31.9 27.9 0.13 0.82 29.8 0.007 0.93

150 36.0 31.7 0.19 0.80 33.7 0.009 0.92

200 56.3 41.8 0.85 0.75 44.6 0.02 0.82

250 67.5 54.0 1.09 0.86 56.3 0.03 0.90

300 71.2 66.7 1.71 0.98 67.5 0.10 0.99

350 80.0 83.6 1.67 0.98 84.6 0.08 0.99

400 100.8 96.9 2.01 0.99 97.6 0.13 0.99

25
Table 3. Parameters of the isotherm models for RR120 dye adsorption on CS-GLA/TNC-25 at
303 K.

Adsorption isotherm Parameter Value

Langmuir qm (mg/g) 103.1

Ka (L/mg) 0.05

R2 0.93

Freundlich Kf (mg/g) (L/mg)1/n 15.2

n 2.6

R2 0.98

Temkin KT (L/mg) 1.09

bT (J/mol) 178.2

R2 0.90

26
Table 4. Comparison of the adsorption capacity of RR120 dye by various adsorbents.

Adsorbents qm References
(mg/g)

Moringa oleifera Seed 413.3 [47]

Chitosan–iron(III) crosslinked 361.9 [48]

Quaternary amine modified orange peel powder 344.8 [49]

Commercial activated carbon 267.2 [50]

Biofilm of cross-linked Chitosan-Ethylene 165.3 [51]

Glycol Diglycidyl Ether

Jatropha curcas shell treated by non-thermal 85.3 [52]

plasma

Functionalized sludge 46.8 [53]

Cross-linked chitosan-GLA/TiO2 nanocomposite 103.1 This study

27
28