Surfaces and Interfaces 18 (2020) 100422

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Surfaces and Interfaces

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Mesoporous Iraqi red kaolin clay as an efficient adsorbent for methylene T

blue dye: Adsorption kinetic, isotherm and mechanism study
Ali H. Jawada,⁎, Ahmed Saud Abdulhameedb
a
School of Chemistry and Environment, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
b
Chemistry Department, College of Science, University of Anbar, Ramadi, Iraq

ARTICLE INFO ABSTRACT

Keywords: An eco-friendly and mesoporous Iraqi red kaolin clay (IRKC) was utilized as an efficient and low-cost adsorbent
Kaolin clay for the removal of methylene blue (MB) dye from aqueous environment. Various analytical techniques were used
Methylene blue dye to investigate the surface area, surface morphology, material crystallinity, and fundamental functional group of
Adsorption mechanism the IRKC. The impact of adsorption operational parameters such as adsorbent dosage (0.02–0.20 g), solution pH
Isotherm models
(2–10), contact time (0–300 min), and initial MB dye concentrations (10–120 mg/L) were studied. The ad-
sorption results were well described by pseudo-first order (PFO) kinetic, and adsorption isotherm was followed
both Langmuir and Freundlich models. The maximum adsorption capacity (qmax) of IRKC for MB dye was found
to be 240.4 mg/g at 303 K. Thus, this work indicates that the IRKC can be applied as a natural promising
adsorbent for MB dye as model of cationic dye from aqueous environment. The MB dye adsorption mechanism
by IRKC can be assigned to several types of interactions such as electrostatic attractions, H-bonding interaction,
and n-π interaction.

1. Introduction effective and environment friendly adsorbents [13-18].

Textile dyes are frequently utilized in unlimited industrial applica-
tions such as textile, printing, paint, food, and cosmetics as a colouring
agent [1]. The discharge of synthetic dyes without treatment into
aqueous environment is one of the most important environmental
problems due to its risks on aquatic life and human's health [2]. Me-
thylene blue (MB) dye is widely used in textile industry for dying
cotton, wood, and leather, in addition to the pharmaceuticals industries
[3]. MB causes harmful effects on human health such as nausea, vo-
miting, heart rate increasing and eye/skin irritation [4,5].
Several treatment methods have been successfully applied to re-
move textile dyes prior to discharge into water such as adsorption [6],
photocatalysis [7], advanced oxidation process [8], and biological
treatment [9]. Adsorption is a prime wastewater treatment method for
dyes removal due to its simplicity of design, non-generation of toxic
materials, low cost and high efficiency [10]. Generally, activated
carbon is the most common adsorbent that commonly utilized for
treatment of wide range of water pollutants [11]. However, activated
carbon requires a high cost for the preparation and regeneration pro-
cesses [12]. Therefore, a great interest has been paid by researchers
towards utilization of natural adsorbent such as natural clays, biopo-
lymers, layered double hydroxides, biochar and waste biomass as cost-
In recent years, various types of natural and modified clays such as
kaolinitic [19], Tunisian smectite [20], Na-montmorillonite [21], sily-
lated bentonite [22], polyamide-vermiculite nanocomposite [23], and
hectorite clay-alginate composite [24] were utilized for removal of dyes
from aqueous environment. The utilization of natural clays as alter-
native adsorbents for the removal of dyes from wastewater offers sev-
eral advantages such as low-cost, high adsorption properties, porosity,
availability, thermal stability, large potential for ion exchange, and
non-toxicity [25, 26]. In this regard, Kaolin is one of the well-known
abundant and low cost natural clays, which is available worldwide in
rocks as crystalline structure [27]. Generally, kaolin is mainly com-
posed of kaolinite, in addition to some minerals such as quartz and mica
[28]. The surface of kaolinite has a constant structural negative charge
resulting from the isomorphous substitution of Si4+ by Al3+in silica
layer, which is considered active adsorption sites for the removal of
dyes from wastewater depending on the pH of the solution [29]. Re-
cently, few studies have been made on utilizing of kaolin and kaolinite
as adsorbents for the removal of water contaminants such as dyes [30],
and metal ions [31].
Therefore, the aim of the current work was to investigate the ability
of Iraqi red kaolin clay (IRKC) as a new low-cost and efficient adsorbent
for removal of cationic dye such as MB dye from aqueous environment.

⁎
Corresponding author.
E-mail addresses: ali288@uitm.edu.my, ahjm72@gmail.com (A.H. Jawad).

https://doi.org/10.1016/j.surfin.2019.100422
Received 10 November 2019; Received in revised form 11 December 2019; Accepted 14 December 2019
Available online 15 December 2019
2468-0230/ © 2019 Elsevier B.V. All rights reserved.
A.H. Jawad and A.S. Abdulhameed
Fig. 1. N2 adsorption-desorption isotherms of IRKC.
The impact of adsorption operational parameters such as adsorbent
dosage, solution pH, contact time, and initial MB dye concentrations
were investigated. The adsorption data were evaluated by different
kinetic and isotherm models. Moreover, the adsorption mechanism of
MB on the surface of IRKC was adequately discussed.
2. Materials and methods
2.1. Materials
Kaolin clay was collected from the west of Iraq and its chemical
composition (by mass%) is SiO2 40.54%, CaO 21.87, Al2O3 7.55%,
Fe2O3 5.73%, MgO 4.65%, K2O 1.5%, Na2O 1.03%, and TiO2 0.53%
[32]. IRKC was grinded and washed with boiled water followed by
filtration process to remove soluble impurities. After that, IRKC powder
was left inside an oven for 24 h at 60 °C. Finally, the IRKC powder
(particle size ≤ 250 µm) was achieved by grinding process of IRKC
particles. Methylene Blue (MB) dye (MW: 319.86 g/mol, assay: ~ 99%,
λmax = 661 nm) was purchased from R&M Chemicals, Malaysia. The
other reagents utilized throughout this study were analytical grade. All
experiments of this research were performed with using ultrapure
water.
2.2. Characterization of IRKC
The characterization of IRKC was performed by various analytical
methods and techniques. The surface area and pore volume of the IRKC
was determined by Micromeritics ASAP 2060 analyzer using nitrogen
adsorption/desorption isotherms at 77 K. Scanning electron micro-
scope-energy dispersive X-ray analyze (SEM-EDX, Zeiss Supra 40 VP,
Germany) was utilized to determine the morphological characteristics
of IRKC before and after adsorption of MB dye. The X-ray diffraction
(XRD, X'Pert PRO, PAnalytical) was used to determine the crystallinity
of IRKC with Cu Kα radiation (λ = 1.54 Å) at 40 kV and 20 mA in 2θ
ranges from 10° to 90° The surface functional groups of IRKC before and
after MB dye adsorption were identified by using Fourier Transform
Infrared (FTIR) spectroscopy (Perkin-Elmer, Spectrum RX I) in the
range of 450 cm−1 to 4000 cm−1. The point of zero charge (pHpzc) for
IRKC adsorbent was calculated based on the reported method [33].
2
Surfaces and Interfaces 18 (2020) 100422
2.3. Batch adsorption experiments
The adsorption experiments of MB dye on IRKC were carried out in
a batch mode. The experiments were performed by using a series of
Erlenmeyer flask (250 mL) containing MB dye solution (100 mL) with
different initial concentrations (10–120 mg/L). The different dosages of
IRKC (0.02 g to 0.2 g) were added to the 100 mL of MB dye solution
with different levels of pHs (2–10), and agitated at fixed shaking speed
of 110 strokes/min at 303 K by using thermostat water bath shaker
(WNB7-45, Memmert, Germany). After adsorption process, the IRKC
was separated from aqueous solutions using syringe filter (0.20 µm),
and the MB dye uptake was calculated by UV–Vis spectroscopy (HACH
DR.. 2800) at 661 nm. Equilibrium isotherms were performed at op-
timum adsorption conditions (temperature = 303 K, adsorbent do-
sage = 0.1 g/100 mL, and pH = 8) by using initial MB concentrations
from 10 to 120 mg/L. The MB dye removal (DR%) and adsorbed
amount of MB dye at equilibrium, qe (mg/g) were determined by fol-
lowing Eqs. (1) and (2), respectively.
(Co Ce )
DR % = × 100
Co (1)
(Co Ce ) V
qe =
W (2)
Where Co (mg/L) is the MB initial concentration while, Ce (mg/L) is
the equilibrium concentration of MB. V (L) is the volume of MB solu-
tion, and W (g) is the weight of IRKC.
3. Results and discussion
3.1. Characterization
3.1.1. Physicochemical properties of IRKC
The pore structure and specific surface area of IRKC were de-
termined by N2 adsorption/desorption isotherms as depicted in Fig. 1.
As can be seen, the N2 physisorption isotherm was type IV according to
the IUPAC classification. This result indicates the presence of meso-
pores in structure of IRKC. The textural properties of IRKC were re-
corded in Table 1. The BET surface area of IRKC was found to be 35.6
(m²/g) as recorded in Table 1, while the mean pore diameter was found
to be 9.54 nm. This result indicates that the IRKC has a high surface
area compare to other natural clays that reported in literature such as
A.H. Jawad and A.S. Abdulhameed Surfaces and Interfaces 18 (2020) 100422

Table 1 at 790 cm−1 can be attributed to -OH deformation linked to Al [30].

The textural properties of IRKC. The FTIR spectrum of IRKC after adsorption of MB dye displays same
Property Value bands in spectrum of IRKC with slight shifting of some bands, indicating
the functional groups of IRKC were involved in the MB dye adsorption.
Furthermore, a new band appeared at 1450 cm−1 can be attributed to
2/
BET surface area (m g) 35.6
Total pore volume (cm3/g) 0.085
the aromatic rings (C = C) of MB dye adsorbed on the surface of IRKC.
Mean pore diameter (nm) 9.54
Vm (cm3 /g) 8.18
3.1.4. SEM-EDX analysis
The surface morphology and chemical composition of IRKC before
and after MB dye adsorption was observed by SEM-EDX analysis.
Fig. 3a and 3b displays the SEM images and their respective EDX
spectra of IRKC before and after MB dye adsorption, respectively. As
can be seen from Fig. 3a, the surface of the IRKC was irregular, het-
erogeneous, and porous surface with various cavities. The EDX spec-
trum of IRKC shows that the IRKC contains the elements C, O, Al, Si and
Ti. The surface of IRKC after the absorption of MB dye (Fig. 3b) was
turned to be less porous with evanescence of crevices on the IRKC
surface, indicating the MB dye molecules were successfully loaded on
the IRKC surface. The EDX spectrum of IRKC after MB dye adsorption
shows that the IRKC contains the elements Fe, C, O, Al, and Si with a
slight increase in content of C can be assigned to the MB dye molecules
that adsorbed on the IRKC surface.

3.2. Adsorption study

3.2.1. Effect of IRKC dosage

The influence of IRKC dosage on removal of MB dye was tested by
varying the adsorbent dosage from 0.02 g to 0.2 g, while the other
adsorption parameter such as solution volume, initial concentration of
MB dye, solution pH, temperature, contact time, shaking speed were
kept constant at 100 mL and 100 mg/L, 5.6, 303 K, 360 min, and 110
strokes/min, respectively. As shown in Fig. 4a, the removal of MB dye
increased from 86.2% to 99.8% with increasing adsorbent dosage from
0.02 g/100 mL to 0.1 g/100 mL. The highest MB dye removal (99.8%)
was obtained at 0.1 g/100 mL, which can be assigned to higher surface
area and/or the adsorption active sites that are available for adsorption
of MB dye molecules. Further increase in adsorbent dosage above 0.1 g
did not show any further improvement in MB dye removal. Therefore,
0.1 g/100 mL was chosen to be an optimum adsorbent dosage for the
further investigations.

3.2.2. Effect of solution pH

Fig. 2. (a) XRD pattern of IRKC, and (b) FTIR spectra of IRKC and IRKC after
MB dye adsorption.
Indian kaolin 13.69 m²/g [29], and Algerian kaolin 21.27 m²/g [30].
Furthermore, IRKC has a mesoporous pore structure according to
IUPAC classification [34].
3.1.2. XRD analysis
The crystallinity of IRKC was investigated by XRD analysis. The XRD
pattern of the IRKC is presented in Fig. 2a. From Fig. 2a, many dif-
fraction peaks at 2θ=12.3°, 19.9°, 24.9°, 35.9°, 38.4°, 45.6°, 55.1° and
62.3° can be observed. This result indicates the presence of kaolinite
Al2Si2O5(OH)4 in the structure of IRKC [35].
3.1.3. FTIR analysis
FTIR analysis was accomplished in order to figure out the available
adsorption functional group on the surface of IRKC before and after MB
adsorption. FTIR spectra of IRKC, and IRKC after adsorption of MB dye
were presented in Fig. 2b. FTIR spectrum of IRKC showed major bands
at ~ 3690 cm−1 and ~ 3430 cm−1, which can be assigned to the
stretching vibrations of OeH, while band at ~ 1640 cm−1 can be as-
signed to the bending vibration of coordinated water [30, 36]. The
peaks at ~ 1110 cm−1 and ~ 990 cm−1 can be attributed to the
stretching vibrations of the Si-O-Si of kaolinite or quartz, while the peak
The effect of solution pH on the adsorption capacity of MB dye on
IRKC surface was performed at different pH levels (pH 2–10) with fixing
others adsorption parameters (adsorbent dosage 0.1 g/100 mL, con-
centration 100 mg/L, and temperature 303 K). It was observed from
Fig. 4b that the increasing in solution pH from 2 to 6 the adsorption
capacity, qt (mg/g) raises from 79.2 mg/g to 88.3 mg/g. The pHpzc
value of IRKC was 7 as shown in Fig. 4c. Generally, at pH value above
pHpzc, the IRKC can be acquired negative surface charges, and as a
result causing a strong electrostatic attraction between negative surface
charge of IRKC and MB dye cations as described in the following
Eq. (3).
IRKC SiO + MB+ IRKC SiO + MB (3)
Therefore, pH ~ 8 was determined to be the best solution pH for the
further applications.
3.2.3. Effect of initial MB concentration and contact time
The influence of initial MB dye concentration and contact time on
adsorption equilibrium was investigated. The adsorption capacity,
qt(mg/g) against time at several initial MB dye concentrations of 10, 20,
50, 80, 100 and 120 mg/L was investigated as depicted in Fig. 5a, while
the other optimum factors such as adsorbent dose (0.1 g), pH of solution
(8), and temperature (303 K) were kept constant. The results showed
that the MB dye uptake on the surface of IRKC in the first 30 min was

3
A.H. Jawad and A.S. Abdulhameed
Fig. 3. SEM images at 3000 x magnification power and EDX spectra of (a) IRKC, and (b) IRKC after MB dye adsorption.
very high (as shown in Fig. 5a) in all concentrations, indicating to a
high surface area and/or active adsorption sites of IRKC. It was ob-
served from Fig. 5a that the quantity of MB dye molecules uptake onto
surface of IRKC raised from 2.2 to 101.6 mg/g with by increasing in the
initial MB dye concentrations from 10 to 120 mg/L. This can be as-
signed to the higher concentration gradient which provides a driving
force to move the MB dye molecules towards active adsorption sites
[37].
3.3. Adsorption kinetic
The non-linear pseudo-first-order (PFO) and non-linear pseudo-
second-order (PSO) kinetic models were utilized to analyze the ex-
perimental data of the MB adsorption on IRKC at different initial MB
concentrations. The non-linear equations of the kinetic models PFO
[38] and PSO [39] are expressed in Eqs. (4) and (5) respectively as
follows:
qt = qe (1 k1 t
) qe = Kf Ce1/ n
exp
qe2 k2 t
qt =
1 + qe k2 t
Where qe (mg/g) is the amount of MB dye adsorbed at equilibrium,
and qt (mg/g) is the amount of MB dye adsorbed at time (t). k1 (1/min)
is the rate constant of PFO, and k2 (g/mg min) is the rate constant of
Surfaces and Interfaces 18 (2020) 100422
PSO. The parameters of kinetic models were recorded in Table 2. Ac-
cording to experimental data (Table 2), it can be concluded that the
adsorption of MB dye molecules by the IRKC adsorbent follows PFO
model due to the higher correlation coefficient (R2) values, and the
calculated qe (qe,cal) values fitted well with the experimental qe (qe,exp)
values. This result indicates that the adsorption of MB dye molecules on
IRKC surface is mainly dominated by physical adsorption [40].
3.4. Adsorption isotherms
Non-linear equilibrium models of Langmuir, Freundlich, and
Temkin were utilized to fit the experimental data. The non-linear
equations of the equilibrium models Langmuir [41], Freundlich [42],
and Temkin [43] are presented in Eqs. (6), (7), and (8), respectively.
qmax K aCe
qe =
1 + K a Ce (6)
(7)
(4)
RT
qe = ln(KT Ce )
bT (8)
(5)
Where qe (mg/g) is the amount of MB dye adsorbed at equilibrium,
Ce (mg/L) is the concentration of MB dye at equilibrium, qmax (mg/g) is
the maximum adsorption capacity, and Ka (L/mg) is Langmuir constant.
Kf (mg/g) (L/mg)1/n is the Freundlich constant, n is the dimensionless
4
A.H. Jawad and A.S. Abdulhameed
Fig. 4. (a) Effect of adsorbent dosage on removal of MB dye, (b) effect of pH on the adsorption of MB dye, and (c) pHpzc of IRKC.
constant indicates to the adsorption intensity. KT (L/mg) is Temkin
constant, T (K) is temperature, R (8.314 J/molK) is the universal gas
constant, and bT (J/mol) is heat of adsorption. The non-linear curves of
the equilibrium models are shown in Fig. 5b. The parameters of equi-
librium models were recorded in Table 3. According to the R2 values
(Table 3) obtained from the isotherm models, it can be concluded that
the adsorption process of MB dye on the surface of IRKC can follow both
Langmuir and Freundlich isotherm models due to high correlation (R2)
0.99 and 0.98, respectively. Moreover, this result also indicates that the
MB dye adsorption was occurred in monolayer and multilayer adsorp-
tion [44]. The maximum adsorption capacity (qmax) of IRKC for MB dye
was recorded to be 240.4 mg/g at 303 K. The qmax of IRKC for MB dye
was compared to other adsorbents as presented in Table 4. Table 4
indicates that IRKC has desirable adsorption property for removal of
cationic dye over other available adsorbents.
3.5. Adsorption mechanism
The surface of IRKC has a potential adsorption sites such as the silanol
(^SiOH) and aluminol (^AlOH) groups, and hydroxyl (-OH) group on
the mineral edges [30, 56]. According to pHpzc of IRKC, the surface of
IRKC acquires a negative charge in alkaline environment by deprotona-
tion of exposed hydroxyl group [29]. Based on that, the adsorption me-
chanism of MB dye on IRKC surface by different types of interactions was
5
Surfaces and Interfaces 18 (2020) 100422
proposed and illustrated in Fig. 6. From Fig. 6, an electrostatic attraction
is considered as the most impactful interaction that can be occurred be-
tween MB dye molecules and surface of IRKC adsorbent. This mechanism
also involves the electrostatic interaction between MB dye cations with
negatively charged available on the IRKC surface. Adsorption mechanism
also includes H-bonding interactions that can be occurred between H
atom available on the surface of IRKC, and N atom in the MB dye struc-
ture. Finally, n-π interaction comes from delocalization of the lone pair
electron of O atoms into the π orbital of the dye aromatic rings. According
to the above, it can be concluded that these interactions were effective in
enhancing adsorption process of MB dye on the surface of IRKC.
4. Conclusion
Iraqi red kaolin clay (IRKC) was successfully applied for the removal
of methylene blue (MB) dye from aqueous environment. The optimum
adsorption conditions of MB dye on the surface of IRKC were de-
termined to be (0.1 g/100 mL), pH ~ 8, and temperature (303 K). The
kinetics data revealed that the adsorption was mainly affected by
physical adsorption. The adsorption capacity of IRKC was 240.4 mg/g
at 303 K for MB dye. The adsorption mechanism included electrostatic
attraction, H-bonding interaction, and n-π interaction. The adsorption
results revealed that the IRKC is an effective and low-cost natural ad-
sorbent for the removal of cationic dyes.
A.H. Jawad and A.S. Abdulhameed Surfaces and Interfaces 18 (2020) 100422

Table 3
Parameters of isotherm models for MB dye adsorption on IRKC at 303 K.
Adsorption isotherm Parameter Value

Langmuir qm (mg/g) 240.4

Ka (L/mg) 2.98
R2 0.99
Freundlich Kf (mg/g) (L/mg)1/n 297.6
n 1.3
R2 0.98
Temkin KT (L/mg) 4.9
bT (J/mol) 101.6
R2 0.86

Table 4
Comparison of the adsorption capacity of MB dye by various adsorbents.
Adsorbents qmax (mg/g) References

Dragon fruit skin 640 [45]

Breadnut peel 409 [46]
Brazilian montmorillonite 300.3 [47]
Rubber leaf 263.2 [48]
Magnetic polyvinyl alcohol/laponite RD 251 [49]
nanocomposite
Amino-functionalized attapulgite nanoparticle 226.24 [50]
Corn cob 216.6 [51]
Breadfruit core 200 [52]
Magnetic chitosan/clay beads 82 [53]
Polyamide-vermiculite nanocomposite 76.42 [23]
Algerian kaolin 52.76 [30]
Omani palygorskite 50.8 [54]
Moroccan Illitic 13.6 [55]
Iraqi red kaolin 240.4 This study

Fig. 5. (a) Effect of the contact time on MB dye adsorption at different initial
concentrations, and (b) adsorption isotherms of MB dye by IRKC (adsorbent
dosage = 0.1 g, pH of solution = 8, temperature = 303 K, agitation
speed = 110 strokes and volume of solution = 100 mL).

Table 2
PFO and PSO kinetic parameters for MB dye adsorption on IRKC.
Co (mg/L) qe exp PFO PSO Fig. 6. Illustration of the possible adsorption mechanism between IRKC surafce
(mg/g) qe cal k1 (1/min) R2 qe cal k2 x 10−2 R2 and MB dye molecules, showing the possible electrostatic attraction, H-bonding
(mg/g) (mg/g) (g/mg min) interaction, and n-π interactions.

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