Journal of Molecular Liquids 333 (2021) 115976

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Adsorption behavior of cationic dye on mesoporous silica SBA-15 carried

by calcium alginate beads: Experimental and molecular dynamics study
Bouhadjar Boukoussa a,b, Adel Mokhtar a,c,⇑, Anouar El Guerdaoui d, Mohammed Hachemaoui a,
Hassan Ouachtak e,f, Soumia Abdelkrim a, Abdelaziz Ait Addi d, Soumia Babou a, Bouchra Boudina a,
Abdelkader Bengueddach a, Rachida Hamacha a
a
Laboratoire de Chimie des Matériaux L.C.M, Université Oran1 Ahmed Ben Bella, BP 1524, El-Mnaouer, 31000 Oran, Algeria
b
Département de Génie des Matériaux, Faculté de Chimie, Université des Sciences et de la Technologie Mohamed Boudiaf, BP 1505, El-Mnaouer, 31000 Oran, Algeria
c
Département Génie des Procédés, Institut des Sciences et Technologies, Centre Universitaire Ahmed Zabana Relizane, Algeria
d
Département de Chimie, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco
e
Faculté des Sciences Appliquées, Ait Melloul, Université Ibn Zohr, Agadir, Morocco
f
Laboratoire de Chimie Appliquée & Environnement, Equipe de chimie Bio-organique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco

a r t i c l e i n f o a b s t r a c t

Article history: This paper describes the fabrication of composites beads based on functionalized SBA-15 materials
Received 2 February 2021 encapsulated in calcium alginate (ALG) which are employed for removing methylene blue (MB). The pre-
Revised 16 March 2021 pared composites beads were characterized by various techniques such as XRD, FTIR, SEM, zeta potential
Accepted 23 March 2021
measurements and TGA. As results, the SBA-15 material was well immobilized in the alginate matrix. The
Available online 29 March 2021
best adsorbent beads were determined by evaluating the kinetics of MB adsorption from aqueous solu-
tions. It has also been established that the hydrogel beads with a pure SBA-15 have a negative surface and
Keywords:
therefore a greater capacity for adsorption of cationic dye compared to the adsorbents beads containing
SBA-15
Alginate
amine-functionalized SBA-15. The combination of two matrices (Pure SBA-15 and alginate) containing
Beads negatively charged surfaces generates excellent properties through the removal of the MB dye. The max-
Adsorption imum adsorption capacity of the ALG-SBA-15 composite was 333.33 mg.g
1. The adsorption well fol-
Methylene blue lowed the pseudo-second-order kinetics and Langmuir isotherm, and was spontaneous endothermic
Isotherm. Molecular dynamic simulations process. The adsorption of MB dye on the ALG-SBA-15 beads could be easily realized through electrostatic
interactions and hydrogen bonding. Furthermore, molecular dynamic (MD) simulations were performed
on pure SBA-15 structure models with different pore diameters to get a glimpse on the dynamic behavior
of MB molecules upon adsorption on the mesoporous material.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction pollutants from waste effluents is adsorption [3,4]. Based on this

technique and these dangerous impacts, scientists always seek to
Recently, industrial discharges constitute a very important combine materials that have different properties for aim to form
source of pollution, which seriously threatens human health and adsorbents with low-cost, environmentally friend, easy to recover
the environment [1,2]. Continued use of these dangerous pollu- [5–9].
tants includes metals, fertilizers, volatile organic compounds, Among the most abundant polysaccharides in the world, alginic
organic halogenated compounds, and dyes that it keeps growing. acid is a carboxylated polysaccharide component with a character-
One of the most important pollutants is dyes; because once dis- istic structure composed of two uronic acids, b-D-mannuronic acid
solved in water, they will sometimes be difficult to treat due to and a-L-guluronic acid [10,11]. Due of their abundance in nature,
their preparation source, complex molecular structure, stability non-toxicity, biocompatibility, biodegradability, hydrophilicity,
in solutions and low biodegradability. Therefore, the most com- and adsorption properties, the alginate is widely used in various
monly and applicable technology to remove these hazardous application field such as adsorption [12], photocatalysis [13],
antibacterial activity [14] and drug release [15,16]. Their main
property is gelation which is carried out by different divalent
⇑ Corresponding author at: Laboratoire de Chimie des Matériaux L.C.M, Université cations and this with an exchange of sodium ions of the guluronic
Oran1 Ahmed Ben Bella, BP 1524, El-Mnaouer, 31000 Oran, Algeria.
acid residues [17]. All divalent cations connect to the a-l-guluronic
E-mail address: mokhtar.adel80@gmail.com (A. Mokhtar).

https://doi.org/10.1016/j.molliq.2021.115976
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

acid blocks between two different chains resulting in a 3D network 36.5–38%), Tetraethyl orthosilicate, (TEOS 99%), (3-
[16–18]. In addition, carboxylic and hydroxyl groups present on Aminopropyle) trimethoxysilane, (3-Aminopropyle) triethoxysi-
alginate make it a favorable candidate to interact with cationic lane, N-(3-Trimethoxysilylpropyl) ethylenediamine, N-(3
dyes via electrostatic interactions and the formation of Trimethoxysilylpropyl) diethylenetriamine were purchased from
biopolymer-inorganic composite can provide interesting combina- Sigma–Aldrich and CaCl2 (93%) from Alfa Aesar. The methylene
tion which might promising for organic dyes adsorption [19–21]. blue as a cationic dye was used in this study, possess an amine
Hydrogel matrix are hydrophilic, three-dimensional arranged, and sulfur groups in its structure (see Table 1). In aqueous medium,
broadly crosslinked polymer chains with extensive swelling capac- MB molecule dissociates into MB+ and Cl
ions.
ity in water, physiological fluids and saline solutions [22], these
interesting properties broaden their application in a variety of 2.2. Characterization techniques and statistical analysis
fields [23–27]. Presently, it has been shown in several studies that
the encapsulation of nanofillers by the biopolymer alginates gener- The structural characterization of pure SBA-15 and their func-
ates new properties compared to the parent materials [28]. The tionalized compounds was examined by a XRD diffraction patterns
encapsulation of zeolites [29,30], mesoporous materials [31], MOFs using Bruker D8 A25 Powder diffractometer (Cu-Ka radiation).
[32], clays [33,34], activated carbon [35], polymers [36] and metal Fourier transforms infrared (FTIR) spectra of all samples were
oxides [16] by alginate has shown significant improvement via the obtained in the range 400–4000 cm
1 using a Bruker ALPHA Plat-
retention of organic and inorganic pollutants. This improvement inum ATR spectrometer. The surface charge of the obtained sam-
was the result of different interactions between the composite ples was measured by zeta potential using Zeta-sizer (model
and the organic pollutants. It is also necessary that this improve- Nano-ZS, Malvern Instruments). The morphology of composite
ment differs from nanofiller to another according to the reactivity beads was obtained by a HIROX SH 400 M SEM-EDX BRUKER scan-
of their surfaces [37]. The specific surface, the surface charge and ning electron microscope (SEM), before analysis the beads were
the presence of the functional groups of nanofillers are the key fac- coated with carbon and attached to sample holders with carbon
tors to improve the performance of the composite. tape. The thermal stability of all samples was evaluated using
Mesoporous silica has known wide applications as adsorbents, LABSYS Evo SETARAM thermogravimetric analysis under nitrogen
catalysts and catalytic support due to their remarkable surface atmosphere in the temperature range 20–900 °C with a heating
properties and their porosities which are higher than zeolites and rate of 10 °C/min.
clays. Due to their negatively charged surfaces, these solids are
considered as effective adsorbents for dye removal. Recently, sev-
2.3. Preparation of samples
eral strategies have been employed on this type of material to
improve their adsorption capacity for cationic dyes. Thus, it was
2.3.1. Pure SBA-15
shown that the encapsulation of mesoporous silica functionalized
The procedure for the preparation of mesoporous silica is simi-
by aminosilane with alginate has shown interesting results for Pb
lar to the work carried out in the literature [44–47]. SBA-15 was
(II) capture [31]. The presence of several functional groups such
synthesized according to the following conditions: initially 0.2 g
as amino, carboxyl and hydroxyl groups can give rise to several
of Pluronic (P123) was dissolved in 15 g of distilled water and stir-
electrostatic interactions and other adsorbent-metal complex
red for 10 min at a temperature of 40 °C, and then 60 g of HCl (2 M)
interactions. In the same context, we are interested in the use of
was added to the Pluronic solution. After homogenization of the
this system with different surface modifications for the capture
mixture, 4.25 g of TEOS was added and then stirred for 2 h at
of MB dye. The computer technology is a good instrument to offer
40 °C. The mixture is brought to a temperature of 100 °C under
insight on involved interactions in the dyes removal [38–40].
autogenous pressure for 48 h. The result material was calcined at
Molecular dynamic (MD) is a powerful tool to provide a better
temperature of 550 °C during 6 h.
insight on the adsorption and dynamic behaviors of small mole-
cules within porous materials up to an atomistic level [41–43].
The present study focused on the preparation of SBA-15-Alginate 2.3.2. Functionalized SBA-15
hydrogel composite beads using CaCl2 as crosslinked agent with pure The mesoporous silica SBA-15 was functionalized according to
SBA-15 and SBA-15 functionalized with mono-,di- and tri-amine. The the method described in the literature using three different
physical characterization of the beads was first studied to explore aminosilanes (mono-, di- and triamine) [45–47]. Firstly, 1 g of cal-
their structural, morphological and thermal properties. This kind of cined SBA-15 was dispersed in 150 mL of toluene and then 1 g of
material was used for the first time for adsorption of MB dye. In the aminosilane was added. The mixture was carried out under reflux
experimental part, the effect of different environmental conditions for 24 h at 60 °C. The final product was recovered by filtration and
such as beads dosage, adsorption time and dye concentration was washed with distilled water and ethanol, and then it was dried at
investigated. Additionally, the adsorption process was studied kinet- 60 °C during 24 h. Three functionalized products were obtained
ically to predict the adsorption rate in orderto understand the adsorp-
tion behavior and the mechanism of adsorption. While for the
Table 1
theoretical part, three SBA-15 mesoporous silica structure models Properties of methylene blue dye.
with different pore diameters (5.7 and 9 nm) were constructed and
Name Methylene blue
subjected to further preparation to get a good agreement with the
experimental material, and then used to investigate theoretically Type Basic dye
Structure
through MD simulations the adsorption of MB molecules.

2. Materials and methods

Chemical formula C16H18ClN3S
Molar mass (g/mol) 319.85
2.1. Chemical reagents Solubility in water High
pH 5.9
Pluronic P123, Sodium Alginate (Sigma Aldrich, low viscosity), pKa 3.8
kmax (nm) 664
Toluene (99.8%), Ethanol (99.8%), Hydrochloric Acid (HCl,
2
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

using three different aminosilanes named (3-aminopropyl) C0: initial concentration of MB solution
trimethoxysilane, N-(3-trimethoxysilylpropyl) ethylenediamine Ceq: Equilibrium concentration of MB solution (after
and N-(3-trimethoxysilylpropyl) diethylenetriamine, the obtained adsorption).
samples were named 1-SBA-15, 2-SBA-15 and 3-SBA-15, V: Volume of the MB dye solution (mL).
respectively. m: The mass of the adsorbent (g).
In order to determine the optimal kinetic and isotherm model,
2.3.3. The alginate functionalized SBA-15 composites beads
the correlation coefficient (R2) was calculated from Origin Lab
The composite beads based on the alginate and SBA-15 or its
software.
modified counterparts were prepared using the following method.
Sodium alginate was dissolved in distilled water (2% w/v). The algi-
nate solution was stirred and left until it becomes homogeneous 3. Results and discussion
solution without any bubbles. Then, 1% of mesoporous silica or
its modified counterparts were added to the alginate solution. 3.1. Characterization of functionalized SBA-15
The mixtures were aspirated by a syringe and deposited in aqueous
solutions of calcium chloride (1 M). The formed spherical beads The XRD patterns of pure SBA-15 and its functionalized coun-
were kept for a moment in a CaCl2 solution, and then it was filtered terparts were presented in Fig. 1S(a). All modified samples show
and washed with distilled water. The obtained composites beads XRD patterns similar to the mesoporous silica SBA-15. As can be
were named ALG@SBA-15, ALG@1-SBA-15, ALG@2-SBA-15 and seen, the materials have the same appearance, an intense peak cor-
ALG@3-SBA-15. The different stages of preparation of the compos- responding to the reflection (1 0 0) with two other diffraction
ite beads are illustrated in Scheme 1. peaks having lower intensities which correspond to the reflection
(1 1 0) and (2 0 0) on the basis of a hexagonal structure [44–47].
2.4. Adsorption investigation However, the intensity of the 100 line was decreased after the
amine functionalization procedure due to the swelling of the
For each test, an amount of MB dye at a concentration of 40 mg/ pores; this line diminished especially since the mass of the organic
L (V = 10 mL) was brought into contact with a certain mass of com- entity is high. Consequently, the lattice parameters of materials
posites, the flasks are then closed and shaken uniformly using a increased in ascending order: 11.3, 11.4, 11.9 and 12.2 nm for
rotary agitator. The adsorption experiments were realized at room SBA-15, 1-SBA-15, 2-SBA-15 and 3-SBA-15, respectively.
temperature (298 K) and at pH 6.5. After reaction time, the mix- FTIR spectra of pure SBA-15 and amine-functionalized SBA-15
tures are simply separated and the adsorption amount of dye samples were shown in Fig. 1S(b). The spectrum of pure SBA-15
was measured by using UV–vis spectrophotometer (Perkinelmer showed the vibrations bands asymmetric and symmetric stretch-
LAMBDA 35). Several parameters were evaluated such as the effect ing characteristics of SiAOASi silanol bridges [44–47], situated
of initial concentration, nature of materials, masses of adsorbents between 1229 and 1057 cm
1. Besides, the located band at
and percentage of SBA-15 material. The measurement of the 962 cm
1 is assigned to the stretching vibrations of free silanol
removal capacity and efficiency was carried out based to Eqs. (1) groups. While the weak band at 1622 cm
1 is assigned to the
and (2), respectively: adsorbed water molecules. For the functionalized materials spec-
tra, several new bands were appeared compared to pure SBA-15.
C 0
C eq The characteristics vibrations of the functional groups of primary,
Removal ð%Þ ¼  100 ð1Þ
C0 secondary and tertiary amine type (CAN) were localized in the
range of 1047 and 1216 cm
1. The low band situated at
ðC 0
C eq Þ  V 1631 cm
1 is attributed to the deformation vibrations of physi-
Q ads ðmg=gÞ ¼ ð2Þ
m sorbed water molecules [44–47].

Scheme 1. Different preparation steps of calcium alginate@mesoporous silica composite beads.

3
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

The physisorbed water and organic matter contents of each 4. Adsorption of MB dye
sample were evaluated using thermogravimetric analysis under
N2 gas flow [45–47]. The TGA curves of parent SBA-15 and the 4.1. Adsorption kinetics
functionalized compounds are given in Fig. 1S(c). As can be seen,
the evolution of the mass loss of all samples takes place in two To study the adsorption kinetics of MB dye on the ALG@SBA-15,
stages. The first stage in the range of 25–100 °C was attributed to ALG@1-SBA-15, ALG@2-SBA-15 and ALG@3-SBA-15 composites
the mass loss of physisorbed water, caused from the elimination beads, operating conditions were 10 mL of MB, 40 mg/L and 1 g
of physically adsorbed water. The mass losses recorded in this tem- of hydrogel beads adsorbent. This study was carried out to deter-
perature range were 5.83, 6.74, 7.55 and 7.64% for pure SBA-15, 1- mine the time required for obtaining adsorption equilibrium and
SBA-15, 2-SBA-15 and 3-SBA-15, respectively. These results prove the quantity of adsorbed MB dye as well as the optimal adsorbent.
that the functionalization improved the hydrophilic character of Fig. 2 shows the adsorption kinetics of methylene blue on compos-
SBA-15. Moreover, the second stage in the range of 100–650 °C ites beads. The evolution curves of the retention capacity of MB dye
was attributed to the degradation of organic molecules caused by on the adsorbents as a function of the contact time have the shape
thermal decomposition of the grafted amine groups from the of the saturation curves. In fact, it can be seen that pollutant fixa-
SBA-15 surface [45–47]. Therefore, the functionalized materials tion curves can be divided into two parts: a first part corresponding
show the losses weight of 15.12; 17.3 and 29.81%, for 1-SBA-15, to a very short phase, where the MB dye was adsorbed very fast
2-SBA-15 and 3-SBA15, respectively. This evolution of mass loss probably due to the availability of the adsorption sites on the com-
was attributed to the percentage of amine groups available in posites beads surface, which carried out in the first minutes. The
SBA-15 surface. The material 3-SBA-15 presents the maximum second part with a medium rapidity shows that the dye adsorbed
mass loss. While for the parent material SBA-15, there is no organic amount changes more slowly, which related to the diffusion phe-
material so recorded mass loss corresponds to the dehydroxylation nomenon with saturation plateau curve form.
of the silanol groups. In all cases, the SBA-15@ALG composite hydrogel was the
best adsorbent for the removal of MB dye, while encouraging
results were obtained with the other SBA-15 hydrogel compos-
3.2. Characterizations of composites beads ites containing amine groups. The adsorbed amounts recorded
on the composite beads yielded better results than the parents
Scanning electron microscopy (SEM) is a technique capable of materials (SBA-15, functionalized SBA-15 and Alginate beads).
producing high resolution images of the sample surface using the As shown in Fig. 3S, the mesoporous silica SBA-15 or its
principle of electron-matter interactions. Fig. 2S shows SEM amino-modified counterparts showed low adsorption capacities
images of SBA-15, ALG and ALG@SBA-15 composite beads. As towards the MB dye. It is well known that SBA-15 functional-
expected, the encapsulation process has not changed the morphol- ized by amines have a positively charged surface and strong
ogy of SBA-15 structure. The parent material and three functional- basicity [45], leading subsequently to repulsion forces between
ized SBA-15 were encapsulated in alginate beads. When the the MB dye and the functionalized SBA-15. But the use of a par-
biopolymer was added to these samples, a distribution of the solid ent material SBA-15 (due to its negatively charged surface) sig-
particles inner the beads was observed, while the aggregation phe- nificantly increased the adsorption capacity of MB dye via
nomenon of some mesoporous particles in the interior of the beads electrostatic attractions and by hydrogen interactions due to
was also observed which is probably due to the viscosity of the presence of the silanol groups (see Fig. 3S). The encapsula-
polymer. tion of SBA-15 functionalized by the amines also gave interest-
The FTIR spectra of composites beads are shown in Fig. 1 (a). ing results and greatly improved the adsorption capacity of MB,
From the spectra, several absorption bands characteristic of meso- but still remains incomparable compared to SBA-15@ALG. This
porous silica type SBA-15 associated with alginate were appeared. difference is strongly linked to the surface of the SBA-15@ALG
The principal vibrations characteristics of these composites beads composite beads which is more negatively charged compared
are generally ranged of 808–3337 cm
1. Moreover, the located to the other composite beads (see Fig. 2b). It should also be
bands at 808 cm
1 correspond to plane deformation vibration. noted that the combination between two negatively charged
While the bands situated in the range of 1026–1047 cm
1 corre- matrices generated a composite with a high negative surface
spond to CAN functional groups. The located bands at 1300, compared to the parent materials, leading to a higher adsorp-
1420, 1593 and 3337 cm
1 were attributed to the CAO, ACH2, tion affinity via MB dye.
NH2 and OAH functional groups, respectively. Consequently, this The pseudo first order (PFO) assumed that the speed of adsorp-
similarity of the band absorption regions of ALG@1-SBA-15, tion at time t is proportional to the difference between the quantity
ALG@2-SBA-15 and ALG@3-SBA-15 samples revealed that the adsorbed at equilibrium (Qe) and the quantity (Qt) adsorbed at this
mixed has physical nature. time and that the adsorption is reversible. The PFO adsorption rate
Fig. 1(b) exhibits the TGA curves of calcined SBA-15, alginate, constant is deduced from the model established by Lagergreen
ALG@SBA-15, ALG@1-SBA-15, ALG@2-SBA-15, ALG@3-SBA15 sam- [48,49]. The speed law is as follows:
ples. As shown in TGA curves, the first zone at low temperature
k
(25–100 °C) corresponds to the weight loss of physisorbed water. LogðQe
QtÞ ¼ LogðQeÞ
t ð3Þ
During this stage, the mass losses of ALG@SBA-15, ALG@1-SBA- 2; 303
15, ALG@2-SBA-15, ALG@3-SBA15 and ALG were 13.76, 16.1, The plot of log (Qe - Qt) as a function of time (t) gives a straight line
20.79, 24.7 and 25.48%, respectively. This shows that the hydrophi- which makes it possible to calculate the adsorption rate constant
lic character has been significantly increased, which probably (K1) and (Qe) for MB dye. The obtained results using the kinetic
caused by the presence of various interactions between the water model of the PFO is shown in Fig. 3a. From this, the experimental
molecules and the composite surface. From the TGA curves, the data of the MB adsorption was found that fitting was not suitable
second zone ranged from 100 to 650 °C. The calculated mass losses for PFO model.
of ALG@SBA-15, ALG@1-SBA-15, ALG@2-SBA-15, ALG@3-SBA15 The pseudo-second-order (PSO) equation is often used success-
and ALG were 21; 25.30; 25.70; 27.66; 51.5%, respectively. These fully to describe the kinetics of the fixing of pollutants on adsor-
losses are due to degradation of grafted amines and the biopolymer bents sites [50]. The linear PSO equation was as follow:
alginate.
4
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

Fig. 1. FTIR (a) and TGA (b) analysis of calcined SBA-15, calcium alginate and composites beads.

Fig. 2. Effect of contact time on adsorption of MB dye (a), Zeta potential measurements of different composite beads obtained at different pH values (b).

Fig. 3. Kinetics adsorption of MB dye on ALG and its modified counterparts, (a) pseudo first order kinetics; (b) pseudo second-order kinetics.

5
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

t 1 1
¼ þ ð4Þ 100
Qt Qe2 K 2 Qe
From the plot of the line t/Qt as a function of time (t), it simplest to 95
describe the adsorption of a dye and deduce the PSO constant (K2)
and the quantity adsorbed at equilibrium (Qe). The linearization

Removal (%)
parameters are illustrated in Table 2 (Fig. 3b). As can be seen, the 90
evolution of t/Qt as a function of time is linear with a determination
coefficient greater than 0.98. We deduce that the adsorption pro-
85
cess of MB perfectly follows the PSO model.

4.2. Influence of the quantity of beads 80

The adsorbent amount has an important effect on the removal

75
of dyes from aqueous solutions [4,14,38]. The different masses of
0,5 1,0 1,5 2,0 2,5
adsorbents used have the objective of studying the effect of the
quantity of beads on the adsorption process of methylene blue Percentage of SBA-15 in the hydrogel beads
and this has been achieved on the various mesoporous materials.
A series of experiments was carried out on different quantities of Fig. 4. Effect of the percentage of SBA-15 in the ALG@SBA-15 composite beads on
the MB adsorption.
adsorbent in the form of hydrogels of (0.5–2.5 g) and with a vol-
ume of 10 mL of MB dye solution with a concentration of 40 mg.
L
1. The suspension is stirred at a stable speed for 360 min and quantity and the concentration of solute in a solvent at a given
at room temperature. The obtained results shows that for the same temperature. For this study, Langmuir and Freundlich model were
concentration of 40 mg.L
1 of MB and during a contact time of used. Langmuir model is applied to the mono molecular adsorption
360 min (see Fig. 4S), the increasing in the mass of the composite of the solute on the surface of the solid and the quantity adsorbed
materials from 0.5 to 2.5 g leads to an increase in the adsorbed is given by the linearization equation:
amount of MB dye. This result can be explained by that the avail-
ability of the sites of adsorption is proportional to the quantity of
adsorbent. Ce Ce 1
¼ þ ð5Þ
Qe Qm QmKL
4.3. Effect of the percentage of SBA-15 in the hydrogel beads
Freundlich empirical model is based on the adsorption on heteroge-
To study the influence of the percentage of SBA-15 in the hydro- neous surfaces. The linearization of this equation implies a passage
gel beads on the adsorption of methylene blue dye, 1 g of polymer of the terms in logarithmic form:
is brought into contact with mesoporous material SBA-15 by vary-
ing the percentage of SBA-15 from 0.5 to 2.5 g. The other experi-
mental conditions were 10 mL  40 mg.L
1 for MB dye and 6 h 1
log Qe ¼ log KF þ log Ce ð6Þ
for contact time. The obtained results were presented in Fig. 4. n
As can be seen, the removal percentages of MB dye are typically
linked to the SBA-15 content in the hydrogel beads. The reported The study of the linearization of the Langmuir and Freundlich mod-
results shows a significant adsorption at higher percentages of els was presented in Fig. 5(a and b), respectively, and their param-
SBA-15 material which stabilizes from 1.5 g of material. Maximum eters were gathered in Table 3.
adsorption is recorded to 2.5 g of SBA-15 by exceeding removal of The adsorption isotherms are simulated very correctly by the
95%.The increase of MB dye adsorption can be explained by the fact Langmuir linear model, which can judge by the value of the corre-
that when the mass of the adsorbent is increased, the number of lation coefficient (R2 > 0.996). Affirm a monolayer and homoge-
adsorption sites is increased, and therefore the elimination of dye neous adsorption; the nf values of Freundlich model are greater
increases. It should also be taken into consideration that the than 1 show that the removal of MB dye was favorable for the
increase in the percentage of SBA-15 generates a more negative physisorption. Overall we find that the Langmuir linear model is
surface and a higher hydrophilic character, which facilitates and the most credible model that best describes our experimental data,
improves the adsorption of the MB dye on this composite [33,34]. with Qmax of 333.33 mg/g and R2 > 0.996. The Langmuir model
shows that the surfaces of samples are energy homogeneous and
4.4. Adsorption isotherms the adsorption of MB on the ALG@SBA-15 beads was monomolec-
ular. These results confirm that the Langmuir model better
Several isotherms models have been proposed for the adsorp- describes the adsorption of Methylene Blue than the Freundlich
tion study expressed by the relationship between the adsorbed model (see Table 3).

Table 2
PFO and PSO model parameters and correlation coefficients for adsorption of MB dye on composites beads.

Adsorbent Qe (mg.g
1) Pseudo-first-order Pseudo-second-order

K1(L.min
1) R2 Qe K2(g.mg
1.min
1) R2
ALG@SBA-15 15.66 0.011515 0.842 15.873 0.00275 0.999
ALG@1-SBA-15 14.89 0.013818 0.977 15.151 0.00197 0.999
ALG@2-SBA-15 14.03 0.011515 0.896 14.492 0.00117 0.999
ALG@3-SBA-15 12.21 0.009212 0.918 12.5 0.00124 0.999
ALG 9.37 0.013818 0.944 9.433 0.00546 0.999

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B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

Fig. 5. Linear modeling by the Langmuir model (a), Linear modeling by the Freundlich model (b).

Table 3
Adsorption isotherms parameters for MB dye onto ALG@SBA-15 composite beads.

Langmuir Freundlich
Qm(mg/g) KL (L/mg) R2 nf Kf (L/g) R2
ALG@SBA-15 333.33 0.027 0.996 1.886 16.443 0.956

5. Theoretical study adjacent OH group was short enough (<2.5 Å) and hence in suffi-
cient proximity for dehydration to occur [41]. The H-bond forma-
5.1. Construction of the initial structures for simulation tion was deduced by plotting the ‘length distribution’ for both of
the H-bonding atom pairs that are formed by adjacent OH groups
MD simulations were carried out on SBA-15 amorphous silica as illustrated in Fig. 7.
models with different pore sizes using Materials Studio software Results from MD simulations conducted at 373 K (see Fig. 6)
package (version 6.0). The molecular models of SBA-15 for the sim- revealed that there are 65, 105 and 145 pairs of adjacent OH on
ulations were built with the similar manner as reported in litera- the fully hydroxylated SBA-15 models of 5 nm, 7 nm and 9 nm pore
ture [41]. The initial model of a-quartz SiO2 (Unit cell parameters diameters respectively, that are close enough to form hydrogen
were a = 4.913 Å, b = 4.913 Å, c = 5.405 Å and a = 90.0, b = 99.0, bond. Therefore, these locations were dehydrated by removing
c = 120.0) was used to construct three SiO2 supercells in the thick- water molecules and the obtained partially dehydrated models
ness of 27.03 Å with different side lengths (in a and b directions) were subjected to geometry optimization carried out the same as
for each superlattice (73.69 Å, 98.26 Å, 117.91 Å). Then, a cylinder aforementioned on the fully hydroxylated SBA-15 structures. Sub-
was carved at the center of each of the constructed supercells along sequently, molecular dynamic (MD) simulation (followed by
the Z direction by removing successive layers of Si and O atoms to length distribution analysis to determine the dehydration loca-
obtain three SBA-15 model structures with pore diameters of 5 nm, tions) was carried out for 100 ps at higher temperature (823 K)
7 nm and 9 nm respectively, which cover the diameter pores range chosen to correlate with the experimental pretreatment tempera-
of the experimental materials for comparison purposes. Thereafter, ture for silica gel. Finally, the equilibrium SBA-15 structures from
the internal surfaces of the created pores were fully saturated with the conducted MD at 823 K was subject to further geometry opti-
hydroxyl groups by completing the vacant bonds on silicon atoms mization after removing the H2O molecules. These models are now
(i.e. Si atoms which have less than 4 bonds) with oxygen atoms and expected to have very similar structures to the real SBA-15 config-
vacant bonds on oxygen atoms (i.e. O atoms which have less than 4 urations and proper to be used in the upcoming simulations.
bonds and 2 bonds) were saturated with hydrogen atoms. The fully Next, the adsorption of MB molecules into the different pore
hydroxylated SBA-15 structures were subjected to geometry opti- sizes was investigated. The conformation of MB molecule is dis-
mization and energy minimization under COMPASS force-field [51] played in Fig. 7 after energy minimization. The adsorption systems
with fine quality using Smart method in the Forcite module. were built by placing 20, 40 and 65 MB molecules in arbitrary posi-
Obtained models of the fully hydroxylated SBA-15 are shown in tions into the pores of 5 nm, 7 nm and 9 nm in diameter, respec-
Fig. 6. tively. In each case, the number of MB molecules was kept in the
The constructed fully hydroxylated SBA-15 models were then same proportion to the square of pore diameter for different mod-
subjected to further preparation to get the dehydrated structures els. The built adsorption systems (i.e. SBA-15 models with the
resulted from the thermal treatment of the experimental material. organic MB molecules) were subjected to dynamic simulations at
Relevant sites where dehydration (removal of water molecules 298 K in canonical NVT ensemble for 1000 ps and with a time step
from SiAOASi linkages) may occur were located from MD simula- of 1 fs using COMPASS force field to obtain the most stable config-
tions (carried out at 373 K for 100 ps at constant volume and tem- urations. During the simulations, the SMART geometry optimiza-
perature (NVT ensemble)) by determining the bonds which are tion algorithm was used with convergence thresholds set to
close enough to form hydrogen bonds. An H-bond is formed when 1  10
5 Kcal.mol
5 for convergence tolerance and 5  10
3
the distance between the O of one OH group and the H of the (Kcal.mol
1)/Å for maximum force. Temperature control was made

7
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

Fig. 6. Schematic illustration of the fully hydroxylated SBA-15 mesoporous silica models with different pore diameters: (a) 5 Å, (b) 7 Å and (c) 9 Å.

by Nosé thermostat and Ewald summation method was used to The self-diffusion coefficient (D) can be used to reflect the
treat van der Waals and electrostatic interactions using a cutoff intensity of MB molecule’s mobility, and therefore their attach-
distance of 15 Å and accuracy of 1  10
4 Kcal mol
1 respectively. ment to the pore walls and can be expressed according to the Ein-
Diffusion of MB molecules within different pores was analyzed stein’s law of diffusion [54,55]:
with mean square displacement (MSD) to get a glimpse on the  
interactions between the organic molecules and silica pore sur- 1 d X MSD 1
D¼ lim Nhjr i ðtÞ
r i ð0Þj2 i ¼ lim ¼ K MSD ð8Þ
faces. MSD, the statistical average of particle trajectories represent- 6N i!j dt i!j t!1 6t 6
ing the average distance between a given particle and other
particles, can be expressed as follow [52,53]:
The self-diffusion coefficient (D) is one-sixth of the slope KMSD of
* + the least squares fitting line of the MSD-time curve.
1 XN
MSD ¼ jr i ðtÞ
r i ð0Þj2 ð7Þ
N i¼1
5.2. Molecular dynamics results

where N is the number of atoms, ri(0) is the particle initial position, The kinetic states of MB molecules into different silica pore
and ri(t) is the position vector at time t. models are displayed at different time steps in Fig. 8.
8
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

Fig. 7. (a) Schematic illustration of H-bonds formation between O of one OH group and H of the adjacent OH group. (b) Optimized MB molecule. Atoms are shown in different
colors: grey: carbon; red: oxygen; blue: nitrogen; white: hydrogen; yellow: sulfur, gold: silicium and cyan: chlorine.

Fig. 8. Snapshots of MB molecules configurations in SBA-15 mesoporous silica with different pore diameters: (a) 5 nm, (b) 7 nm and (c) 11 nm at various times of dynamic
simulations.

As shown from the snapshots of the conducted simulations, the The plots of simulation time elapsing from 0 to 1000 ps, versus
MB molecules in all the pores of different sizes moved toward the the average mean square displacement (MSD) of all MB molecules
pore walls to reach a their stable rearrangements within 750 ps, within different pore sizes are shown in Fig. 4 and the
which may be ascribed to the strong interaction between the OH corresponding diffusion coefficients were calculated and presented
groups of the silica surface and guest molecules. in Table 4.
9
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

Table 4
Average diffusion coefficients of MB molecules within
mesoporous silica of different pore sizes.

Pore size (nm) Diffusion coefficient (10
10m2/s)

5 4.34
7 7.97
9 12.14

Fig. 10. Proposed adsorption mechanism of MB dye on ALG@SBA-15.

in crosslink process. As can be seen, the mechanism is related to

two distinguish interactions, first one was attributed to the electro-
static attractions forces, this is formed from the difference between
the charges of the SBA-15 surface material and the MB molecules.
The second one was attributed to the hydrogen bonding between
the amines groups of dye and the OH groups present in adsorbent
Fig. 9. Average MSD values for MB molecules interacting with different meso-
beads [6].
porous silica models over 1000 ps at 298 K.

5.4. Comparative study

From Fig. 9, it can be seen that the average MSD of MB mole-
The maximum adsorption capacity (Qmax) of the ALG@SBA-15
cules in the 5 nm-sized pore is significantly less than that of
composite beads was compared with two types of commonly
7 nm and that the latter in turn has lower average MSD values than
adsorbents reported in the literature. Table 5 present two separate
those correspond to the MB molecules within the 11 nm-sized
sections: the first one contained alginate based adsorbents and the
pore,indicating that average MSD values increase as the pore sizes
second one contained SBA-15 based adsorbents. The adsorption
increased. The observed MSD behavior of MB molecules may be
capacity of MB dye on ALG@SBA-15 is greater than the two types
ascribed to larger pores able to provide more free volume for the
of adsorbents mentioned in the table. However, Qmax is higher than
migration of these molecules.
From the data presented in Table 4, it was observed that the dif-
fusion coefficients increased as the pore diameter expanding in Table 5
accordance with the MSD results. The low MSD and diffusion coef- Comparative study via the adsorption capacity of MB dye carried out by different
ficient (4.34  10
10m2/s) values were recorded in the case of adsorbents.
5 nm-sized pore suggesting that MB molecules strongly interact Alginate based adsorbent Qmax Ref
with silica surface and consequently their movement is more (mg/g)
restricted within this pore. Herein, it seems that the limited free Alginate Ca-alginate Sugarcane bagasse 71.21 [56]
volume provided by the small pore size caused remarkable steric based Poly(vinyl alcohol) sodium alginate- 137.2 [57]
hindrance of the guest molecules and therefore limited their adsorbent chitosan-montmorillonite nanosheets
migration. When the pore sizes were increased to 7 nm and hydrogel beads
Hydroxyapatite-sodium alginate 142.850 [58]
9 nm, more space is now available for the movement MB mole- Graphene oxide/calcium alginate 181.81 [59]
cules. This was reflected on the MSD and the diffusion coefficient composites
values (7.97  10
10m2/s and 12.14  10
10m2/s for 7 and 9 nm Reduced monolithic graphene oxide- 192.3 [60]
respectively) which were significantly increased. sodium alginate (RGO-SA)
Alginate-Whey composite beads 220 [19]
Mesoporous activatedcarbon-alginate 230 [35]
beads
5.3. Proposed adsorption mechanism
SBA-15 based SBA-15 41 [61]
Adsorbent PPy/SBA-15(1%) 58.82 [62]
In this study, we have shown that the functionalization of SBA- LS/N-SBA-15 62.89 [63]
15 by different amines changes the charge on the surface of the PVA/SBA-15(30%) 76.92 [64]
material. Consequently, the best adsorbent for the MB dye was Al-incorporated SBA-15 (GA005) 83.1 [61]
Mesoporous magnesium silicate-silica 283 [65]
the ALG@SBA-15 hydrogel beads. All the possible interactions Ti-doped SBA-15 208.3 [66]
between ALG@SBA-15 composite beads and MB molecules are pre- Coal fly ash-derived mesoporous silica 323.62 [67]
sented in the Fig. 10. The removal mechanism of MB dye can be material (CFA-MS)
suggested by the electrostatic attractions forces and hydrogen’s ALG@SBA-15 composite beads 333.33 This
work
bonding generated from the SiAOH and frees SiAO
present in
SBA-15 and some OH groups of alginate which did not intervene
10
B. Boukoussa, A. Mokhtar, A. El Guerdaoui et al. Journal of Molecular Liquids 333 (2021) 115976

the alginate adsorbents while it is slightly higher than the SBA-15 Declaration of Competing Interest
adsorbents. For this, it can be say that SBA-15 has improved the
adsorption capacity of the composite. After synthesizing an adsor- The authors declare that they have no known competing finan-
bent by SBA-15 and ALG, the composite beads have not only cial interests or personal relationships that could have appeared
improved the adsorption capacity of the materials, but they also to influence the work reported in this paper.
have the property of being easily recovered from the aqueous solu-
tion by applying the conventional separation method. The results Acknowledgment
reveal that ALG@SBA-15 composite is an effective adsorbent for
removing cationic dyes. The authors thank DGRSDT and the Ministry of Education and
Scientific Research of Algeria for funding this work.

6. Conclusions
Appendix A. Supplementary data
In conclusion, a series of adsorbents beads were prepared in
Supplementary data to this article can be found online at
order to evaluate them to MB dye removal from an aqueous solu-
https://doi.org/10.1016/j.molliq.2021.115976.
tion. All the prepared adsorbents beads were characterized by XRD,
FTIR, SEM, Zeta potential measurements and TGA analysis. These
results showed that mesoporous silica SBA-15 and its modified References
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