J Mater Sci

Composites
COMPOSITES

Preparation of highly hydrophilic PVA/SBA-15

composite materials and their adsorption behavior
toward cationic dye: effect of PVA content
Zakaria Abid1, Aboubakr Hakiki1, Bouhadjar Boukoussa1,2,* , Franck Launay3,
Hadj Hamaizi1, Abdelkader Bengueddach1, and Rachida Hamacha1

1
Laboratoire de Chimie des Matériaux L.C.M, Université Oran1 Ahmed Ben Bella, El-Mnaouer, BP 1524, 31000 Oran, Algeria
2
Département de Génie des Matériaux, Faculté de Chimie, Université des Sciences et de la Technologie Mohamed Boudiaf,
El-Mnaouer, BP 1505, Oran, Algeria
3
Sorbonne Université, CNRS UMR 7197, Laboratoire de Réactivité de Surface, LRS, Campus Pierre et Marie Curie, 75005 Paris, France

Received: 1 November 2018 ABSTRACT

Accepted: 4 February 2019
 Springer Science+Business
Media, LLC, part of Springer
Nature 2019
This work focuses on the preparation of highly hydrophilic polyvinyl alcohol/
SBA-15 composites by impregnation method. In order to study the effect of
polyvinyl alcohol (PVA) on the structural, textural properties of composites,
several percentages of PVA were impregnated into the surface of the meso-
porous silica SBA-15. The obtained composites were characterized by different
physicochemical techniques such as X-ray diffraction (XRD), Fourier transform
infrared spectroscopy (FTIR), nitrogen adsorption-desorption at 77 K adsorp-
tion–desorption at 77 K, thermogravimetric analysis (TGA) and scanning elec-
tronic microscopy (SEM). The obtained results showed that the structure of
SBA-15 was swollen after PVA impregnation, confirming the dispersion of PVA
inside the pores. The higher percentages of PVA lead to the decrease in the
lattice parameter which results in the formation of PVA aggregates outside the
surface. TGA analysis has shown improvement in the hydrophilic character of
resulting composite, and this affinity via the water molecules is the result of the
increase in number of –OH groups. The obtained composites were used for the
adsorption of methylene blue (MB) dye. Effects of contact time, PVA content,
adsorbent mass and initial dye concentration were investigated and discussed in
terms of adsorption capacity. The experimental data were fitted by pseudo-first-
order and pseudo-second-order models and verified by the Langmuir and
Freundlich isotherms. The results showed that the adsorption of MB dye on
composites followed Langmuir adsorption isotherm models and pseudo-sec-
ond-order kinetics. The best adsorption capacity of MB dye recorded is
* 77 mg/g for composite PVA/SBA-15(30%).

Address correspondence to E-mail: bbouhdjer@yahoo.fr; bouhadjar.boukoussa@univ-usto.dz

https://doi.org/10.1007/s10853-019-03415-w

Introduction
The problem of water pollution is undoubtedly one
of the most worrying aspects of the degradation of
the natural environment [1–4]. This is defined as a
degradation of water quality caused by discharges
from the entire surface of the territory and transmit-
ted indirectly to the aquatic environment. The
industrial activities present a very important source
of pollution, which can pose a serious threat to
human health and its environment [1–4]. In particu-
lar, we mention water pollution since it is the most
important raw material on our planet for humans,
animals, plants and microorganisms. One of the
major pollutants is dyes; once they are dissolved in
water, they will sometimes be difficult to treat
because dyes have a synthetic origin and a complex
molecular structure.
Organic synthetic dyes are compounds used in
many industrial sectors such as foods, papers, phar-
maceutical, leathers, cosmetics, plastics and espe-
cially in the textile industries [5–9]. The presence of
dyestuffs in textile waste presents a real danger to the
environment because of its stability and low
biodegradability. The discoloration of textile rejects
was the subject of many studies. We can proceed
with different methods of treatment, physical,
chemical and biological to treat and discolor polluted
effluents such as coagulation and flocculation [10],
chemical oxidation [10], adsorption [10], photocatal-
ysis [11, 12], decolorization [13], biodegradation [13],
detoxification [13], filtration membrane [14], ozona-
tion [15], electrochemical methods [16] and ion
exchange [17]. Adsorption remains the most used
and most favorable technique for the removal of
dyes, and among the most useful adsorbents include
active carbon [18], clays [19], zeolites [20] and meso-
porous materials [21, 22].
During the last decades, a new family of meso-
porous solids (such as MCM-41, HMS, SBA-15, SBA-
1,…etc) has been widely studied by many researchers
for various applications including adsorption of
metal ions and organic pollutants [21–24]. Meso-
porous materials, especially those based on meso-
porous silica, have attracted enormous attention
[25–31]. Particularly, the mesoporous Santa Barbara
Amorphous-15 (SBA-15) is one of the best candidates
due to its remarkable properties such as regular pore
structure, adjustable pore diameter, large surface and
J Mater Sci
high thermal and hydrothermal stability
[25, 27, 31–33]. However, because of their inert
framework, the mesoporous silicas cannot be used
without surface modification [22, 25, 27, 31]. Among
the methods proposed to solve this problem, there
are the dispersion of metal [27], incorporation of a
metal [34], dispersion of polymers [22, 25, 27, 28],
functionalization by the organic moieties [31].
An interesting way to overcome this major defi-
ciency based on the use of composites polymer/me-
soporous silica [25, 27, 28], in several areas more
particularly for wastewater treatment [22, 35–40]. The
dispersion of the polymers in the silicate matrix
generates interesting properties such as the control of
degree of hydrophobicity, improvement in the ther-
mal stability, heat resistance, gas barrier properties,
electrical and electrochemical behavior, change in the
charge of the surface, making it an excellent adsor-
bent for a variety of dyes.
By examining the literature, we find that the
adsorption of dye on composites polymers/SBA-15
has barely been tackled. Our choice is targeted on the
use of polyvinyl alcohol (PVA) for the preparation of
composites due to its interesting properties such as
non-toxicity, non-carcinogenicity, biocompatibility,
good film-forming ability and processability. It is
used in several fields such as pharmaceutical, oph-
thalmic lubricant, variety of coatings, cosmetics,
papermaking, textiles and other products. The main
objective of this work is the preparation of a new
composites PVA/SBA-15, and as a new application,
these samples were tested for elimination of methy-
lene blue (MB) dye.
Experimental
Preparation of SBA-15
The mesoporous silica SBA-15 was prepared follow-
ing the protocol described in the literature [22, 25, 41].
In a beaker, 2 g mass of triblock copolymer (Pluronic
P123, Aldrich) and 15 g of H2O were mixed with
stirring for 15 min, and then 60 g of hydrochloric acid
2 M (HCl 37%, Sigma–Aldrich) was added, the mix-
ture was stirred for 20 min at 40 C, and then 4.3 g of
tetraethyl orthosilicate (TEOS, Aldrich, 98%) was
added dropwise. The mixture was stirred at 40 C for
20 h and then hydrothermally treated at 100 C for
48 h. The obtained solid was filtered, washed and
J Mater Sci
dried. To remove the surfactant and to release the
porosity, the material SBA-15 was calcined under air
at 550 C for 6 h.
Preparation of composite PVA/SBA-15
Approximately 0.5 g of calcined mesoporous silica
SBA-15 was dispersed in 50 ml of distilled water
under stirring for 5 min, after various mass percent-
ages of polyvinyl alcohol (PVA, Aldrich, Mw &
130000) (10, 30, 50 and 75%) were dispersed in the
reaction mixture and then stirred for 24 h at room
temperature. The obtained composites were filtered
and dried in an oven at 60 C for 24 h (see Scheme 1).
Adsorbents characterization
X-ray powder diffraction patterns of composites were
obtained by Bruker AXS D8 diffractometer using Cu–
Ka radiation in the 2h range of 0.5–6. FTIR spectra
of composites PVA/SBA-15 in the range of
500–4000 cm-1 were collected on a Bruker Alpha
Platinum ATR. Thermogravimetric analysis (TGA)
was performed by means of a TA Instruments-Waters
SDT Q600 analyzer under flow of a nitrogen gas. The
nitrogen adsorption/desorption isotherms were
obtained at - 196 C on ASAP 2020 Micromeritics.
The obtained materials were outgassed at 80 C for
10 h prior to the adsorption measurements. The SEM
images of composite were observed by FEI Philips
XL30 field emission gun environmental scanning
electronic microscopy (FEGESEM).
Scheme 1 Possible mechanism for the formation of composite PVA/SBA-15.
Adsorption of MB dye on composite PVA/
SBA-15
The dye adsorption was well described in our pre-
viously published work [22]. Briefly, all the experi-
ments were performed in duplicate at room
temperature and the calculated value of the adsorbed
quantity corresponds to the average value of two
experiments; the pH value of MB dye was close to 4.5.
Adsorption of MB dye was performed in beakers of
50 mL using 20 mg of adsorbent with 20 mL of dye
solution (40 mg/L). At the end of the adsorption
process, the supernatant was recovered by centrifu-
gation and analyzed by spectrophotometry (UV–vis
Specord 210 Analytik Jena). The adsorption percent-
age of MB dye was calculated by Eq. (1), and the
adsorbed amount qe (mg/g) was calculated by
Eq. (2), where C0 (mg/L) is the initial concentration,
Ci (mg/L) is the final concentration, Ce (mg/L) is the
equilibrium concentration of MB dye, m (g) is the
mass of adsorbent and V (L) is the volume of
solution:
C0  Ci
Removalð%Þ ¼  100% ð1Þ
C0
C0  Ce
qe ¼ V ð2Þ
m
Results and discussion
Structural characterization
The XRD patterns, measured between 2h & 0.5–6 of
composite PVA/SBA-15 obtained at different per-
centages of PVA, are shown in Fig. 1. The XRD pat-
terns of the composites (PVA/SBA-15) clearly show
 J Mater Sci

400000 leading to the formation of aggregates on the outer

PVA/SBA-15(10%)
PVA/SBA-15(30%)
surface.
350000
PVA/SBA-15(50%)
300000
PVA/SBA-15(75%) Fourier transform infrared spectroscopy
Intensity (a.u)

250000
5.10
200000
150000
100000
50000
0 1 2 3 4 5
2θ (°)
Figure 1 XRD patterns of composites PVA/SBA-15.
three characteristic peaks of the mesoporous silica
[22, 25, 31, 34, 41]. All samples exhibit a hexagonal 2D
(p6 mm) pore arrangement which confirms the for-
mation of well-ordered mesoporous silica with
hexagonal regularity [22, 25, 31, 34, 41]. The intense
peak is located at 2h = 0.93 and attributed to the
reflection (100) followed by two less intense peaks
located between 1.55 and 1.76 corresponding to the
reflections (110) and (200), respectively. This also
means that the structure of the mesoporous silica is
maintained after the PVA treatment. The intensity of
peak (100) slightly decreased with increasing the
percentage of PVA due to the inclusion of the poly-
mer in the channels [22, 25]. The peaks indicate that
there was substantial change in pore structure after
PVA addition. We note a displacement of the peak
(110) toward the small angles for composites PVA/
SBA-15 (10%, 30% and 50%) which is explained by an
increase in the distance d100 as shown in Table 1.
However, we find that the composite PVA/SBA-
15(75%) has the lowest lattice parameter, probably
due to the high concentration of PVA subsequently
4
Figure 2 represents the infrared spectra of PVA and
composites PVA/SBA-15 with different percentages
of polyvinyl alcohol and shows several characteristic
adsorption bands of the mesoporous silica-type SBA-
15 associated with the polyvinyl alcohol. The wide
adsorption band at 3409 cm-1 corresponds to the
stretching vibrations of the OH groups associated
with the polymer (PVA). The band at 3778 cm-1 is
6
characteristic of the O–H bond elongation vibrations
of physisorbed water and also attributed to Si–OH
surface silanol groups. The bands at 1068 cm-1 and
800 cm-1 are assigned to the asymmetric and sym-
metric elongation vibrations of Si–O–Si, respectively.
The increase in the intensity of these bands is due to
symmetric elongation vibrations of Si–O at 800 cm-1.
We also note the presence of an intense band
assigned to the deformation of the angle (O–Si–O)
tetrahedral SiO4 at 445 cm-1. The low band at
1635 cm-1 is attributed to the deformation vibrations
of physisorbed water [22, 25, 31], and the low bands
at 1843–2350 cm-1 indicate C–H bonding of PVA.
The spectra of PVA also show a broad band of O–H
stretching at 3462 cm-1 and a strong band of C–O
stretching acetate groups at 1638 cm-1 [42]. The
bands at 2921, 1431 and 1073 cm-1 are associated
with the C–H and C–O–C stretching vibrations and
C–H flexion, respectively [43]. The bands at
2946–2907 cm-1, 1736 cm-1 are assigned to the
vibrations of –CH3, –CH2 asymmetric and –CH ali-
phatic, respectively.
Thermogravimetric analysis (TGA)
Thermogravimetric analysis makes it possible to
evaluate the losses of mass generated by a heat

Table 1 Structural and

textural characteristics of Samples PVA (%)a d100 (Å) a0 (Å) SBET (m2/g) VMeso (cm3/g)
composite PVA/SBA-15
PVA/SBA-15 (10%) 4.8 94.76 109.42 739 1.4
PVA/SBA-15 (30%) 11.3 99.45 114.84 728 1.3
PVA/SBA-15 (50%) 29.2 107.04 123.61 547 1
PVA/SBA-15 (75%) 30 92.85 107.22 547 1
a
percentage of PVA determined by the TGA analysis
dhkl interplanar distance, d100 = k/2 sinh
a0 lattice parameter, a0 = dhkl (2/H3) = d100 (2/H3)
J Mater Sci

1,0 (a) 100

0,9

0,8
80
Transmittance (a.u)

0,7

Weight loss (%)

0,6 60
0,5 PVA/SBA-15(10%)
PVA/SBA-15(30%)
0,4 40
PVA/SBA-15(50%)
SBA-15 Calcined
0,3 PVA/SBA-15(75%) PVA/SBA-15(10%)
PVA PVA/SBA-15(30%)
0,2 20
PVA/SBA-15(50%)
0.1
0,1 PVA/SBA-15(75%)
PVA
0,0 0
4000 3500 3000 2500 2000 1500 1000 500 0 100 200 300 400 500 600 700 800
-1 Temperature (°C)
Wavenumbers (cm )
(b) 1,2
Figure 2 FTIR spectra of PVA and composites PVA/SBA-15. SBA-15 calcined
PVA/SBA-15 (10%)
1,0 PVA/SBA-15 (30%)
treatment under gas flow (N2). This technique makes PVA/SBA-15 (50%)
it possible to quantify the physisorbed water and PVA/SBA-15 (75%)
0,8 PVA
organic matter contents for each sample. Figure 3
shows the mass loss of calcined SBA-15 (parent
dTG

0,6
material), PVA and composites PVA/SBA-15.
According to the TGA/dTG Curves, the mass losses
0,4
of our samples can be divided into two zones of
degradation. The first zone is located at low tem-
0,2
perature (17–100 C) corresponding to the dehydra-
tion of physisorbed water; in this temperature range,
0,0
the SBA-15 has a mass loss of about 12.87%. A large 0 100 200 300 400 500 600 700 800
mass loss was recorded for the composites PVA/ Temperature (°C)
SBA-15, and approximately 50.5%, 53.54%, 30.87%
and 48.98% of mass losses were recorded for the Figure 3 Thermogravimetric analysis of different synthesized
composites 10%, 30%, 50% and 75%, respectively. materials. a TGA, b dTG.
This shows that the hydrophilic character was sig-
nificantly increased probably due to several interac- Textural properties
tions between the H2O molecules and the –OH
The nitrogen adsorption–desorption isotherms of
functions of polyvinyl alcohol (PVA). In the case of
composite PVA/SBA-15 are shown in Fig. 4. All the
composite PVA/SBA-15, the second mass loss is
isotherms are of type IV, according to the IUPAC
about 100–500 C due to polymer degradation steps
classification [44], which are characteristic of meso-
[42]. The mass loss of PVA increases in the following
porous materials. At low relative pressures P/
sequence 4.8%, 11.3%, 29.2% and 30% for composite
P0 & 0–0.6, there are the formations of a monolayer
10%, 30%, 50% and 75%, respectively. According to
filling in micropores and on the outer surface of
these results, the obtained composites showed a
solids. The large increase in adsorbed volume at rel-
higher thermal stability compared to the pure PVA,
ative pressures P/P0 & 0.6–0.8 is associated with the
which is due to the strong interactions between the
capillary condensation of nitrogen inside the chan-
PVA and the surface of SBA-15 leading to the for-
nels and therefore the volume filling of the meso-
mation of stable composite material.
pores. In this pressure range, the isotherms are
irreversible, having H1-type hysteresis between the
curves recorded in adsorption and desorption, which

1600
PVA/SBA-15(10)
PVA/SBA-15(30)
1400
Adsorbed amount (cm /g STP)
PVA/SBA-15(50)
1200 PVA/SBA-15(75)
3
1000
800
600
400
200
0 on composites PVA/SBA-15, the experiments were
0,0 0,2 0,4 0,6
Relative pressure(P/P0)
Figure 4 Nitrogen adsorption/desorption isotherm of composite
materials.
confirms that the pore size is sufficiently large. At
higher relative pressures P/P0 [ 0.8, a multilayer of
nitrogen is formed on the outer surface. The values of
the total pore volume and the specific surface area of
the mesopores can be determined from nitrogen
adsorption–desorption data. On the other hand, the
introduction of the PVA polymer into the calcined
SBA-15 materials significantly decreases the pore
volume and the BET specific surface area. This phe-
nomenon is probably due to the presence of PVA
inside the mesoporous channels. At low percentages
of PVA, polyvinyl alcohol can form a thin film in the
inner surface of SBA-15. The possible interactions in
this case are van der waals and hydrogen bonding.
The formation of thin films in the inner surface also
leads to a slight decrease in the BET surface and the
pore volume. On the other hand, the use of higher
percentages of PVA (see Table 1) led to a sharp
decrease in the BET surface and the pore volume,
suggesting the formation of thin films and different
forms of PVA aggregates subsequently blocking the
pores of SBA-15.
Morphology
Figure 5 shows SEM images of SBA-15 and compos-
ite PVA/SBA-15(30%). The SEM image of the mate-
rial SBA-15 reveals a morphology in hexagonal form
that is very well visualized, and the particles are
identical; Fig. 5 represents elongate aggregates
(35 9 5 lm2) made from primary particles in the
form of long rods (1 lm). After the impregnation of
J Mater Sci
polyvinyl alcohol, it is observed that the shape of the
SBA-15 is still maintained in a wider cylindrical
shape of 2 lm, which also shows the impregnation of
polyvinyl alcohol takes place inside the pores of the
SBA-15.
Adsorption of MB dye
Kinetic study
200 In order to study the adsorption kinetics of MB dye
0,8 1,0 carried out under the same operating conditions;
20 ml of dye solution MB (40 mg/L) was stirred in
the presence of 20 mg of adsorbent. The study of
adsorption of MB dye on an adsorbent allows us to
examine the influence of contact time on its adsorp-
tion capacity. This study was conducted to determine
the time required for the adsorption equilibrium and
the adsorbed amount of MB dye. The results of the
adsorption kinetics of MB dye on composite materials
(PVA/SBA-15) are shown in Fig. 6a. The evolution of
the adsorption capacity of MB dye on different
adsorbents used as a function of the contact time has
the shape of the saturation curves.
In fact, it can be seen that the fixation curves of MB
dye can be divided into two parts: The first part of the
kinetics corresponds to a very short phase, where the
MB dye fixation is very fast, which is carried out in
the first minutes of adsorption for 30 min corre-
sponding to the external mass transfer on the surface.
The second phase is characterized by an average
adsorption rate where the adsorbed quantity evolves
more slowly due to the diffusion phenomenon, which
is well represented by a saturation plateau. The
adsorption capacities of MB dye change according to
the percentage of PVA in each sample (see Fig. 6b).
The samples containing the lowest percentage of
PVA showed a better adsorption capacity toward MB
dye, while those containing the higher percentages of
PVA exhibited the lower adsorption capacities. The
higher percentages of PVA can form aggregates of
PVA on the outer surface which render a tortuous
diffusion of the MB dye inside the mesoporous silica.
As shown in Fig. 6b, the best adsorption capacity was
obtained by the composite PVA/SBA-15(30%), which
is probably due to the presence of the thin layers of
PVA in the internal surface leading thereafter to
greater diffusion of MB dye inside the nano-pores.
J Mater Sci
Figure 5 SEM images SBA-
15 and composite PVA/SBA-
15(30%).
This affinity for MB dye is also expressed by the
higher dispersion of active sites on the surface of
SBA-15, suggesting that the dispersion of PVA thin
films results in the formation of high sites number in
the mesoporous silica SBA-15.
Kinetics modeling
Pseudo-first-order model
In this model, it is assumed that the adsorption rate at
time t is proportional to the difference between the
equilibrium adsorbed amount (qe) and adsorbed
amount at time t (qt) and that the adsorption is
reversible. The first-order adsorption rate constant is
derived from the Lagergren model. This model is
described by the following equation [45]:
K1
Logðqe  qt Þ ¼ Logðqe Þ  t
2:303
K1 is the rate constant; qt and qe are the adsorbed
amounts of MB dye at t time and at equilibrium,
respectively. The plot of log (qe - qt) as a function of
time (t) gives a straight line which makes it possible
to calculate the adsorption rate constants K1 and qe
for MB dye; the obtained results using the pseudo-
first-order kinetic model are shown in Fig. 1S, and the
linearization parameters are shown in Table 2.
According to this model, we find that the fitting of
experimental data by the pseudo-first-order model is
not suitable to describe the adsorption of MB dye.
Pseudo-second-order model
The pseudo-second-order model is described by the
following equation [46]:
t 1 t
¼ þ
qt q2e  K2 qe
This model is often used successfully to describe the
kinetics of the binding reaction of pollutants on
adsorbents. This is the simplest way of describing the
adsorption of a dye, and one can deduce the pseudo-
second-order constant (K2) and the amount adsorbed
at equilibrium (qe) from the plot of the right t/qt as a
function of time (t). We note on the different plots
that the evolution of t/qt as a function of time is linear
with a coefficient of determination greater than 0.98
(see Fig. 7). The linearization parameters are shown
in Table 2. From the results summarized in Table 2, it
is clear that the adsorption kinetics of MB dye per-
fectly follows the model of the pseudo-second order
than first order.
 J Mater Sci

(a) 100 8
PVA/SBA-15(10%)
PVA/SBA-15(30%)
PVA/SBA-15(50%)
80
6 PVA/SBA-15(75%)

60
Qads (%)

t/Qt
4

40

PVA/SBA-15(10%) 2
20 PVA/SBA-15(30%)
PVA/SBA-15(50%)
PVA/SBA-15(75%)
0 0
0 20 40 60 80 100 120 140 160 180 0 40 80 120 160 200
Time (min) Time (min)
(b) 100 Figure 7 Application of the pseudo-second-order model to the
adsorption of MB on composite materials.

80
adsorption process, and a series of experiments were
carried out at different masses (10 mg, 20 mg, 30 mg,
60 40 mg, 50 mg) and with a volume V = 20 mL of the
Qads (%)

MB dye solution (40 mg/L). The suspension was

maintained at a constant stirring rate for 60 min at
40
room temperature. There was a significant effect of
the adsorbent mass on the adsorbed quantity of MB
20 dye [22], and it appears through these results that for
the same conditions, an increase in the mass of
composite materials from 10 to 50 mg results in an
0
0 5 10 15 20 25 30 increase in the adsorbed amount of MB dye (see
PVA (%) Fig. 8). For example, the adsorbed amount of MB dye
increases from 85 to 99% when the mass of composite
Figure 6 a Adsorption kinetics of MB dye on composite PVA/SBA-15(30%) increases from 10 to 30 mg,
materials, b effect of PVA content on the adsorption capacity of
respectively. The maximum adsorption capacity of
MB dye.
MB dye is 98% for the composite PVA/SBA-15(30%).
The increase in the percentage of adsorption can be
Influence of adsorbent mass
explained by the increase in the adsorbent mass, the
The different masses of adsorbents used are intended number of adsorption sites was increased and thus
to study the effect of this parameter on the MB dye the adsorption of the MB dye will be important [22].

Table 2 Kinetic parameters of pseudo-first order and pseudo-second order for adsorption of BM dye

Samples Pseudo-first order Pseudo-second order

2
Qe (mg/g) Qcal (mg/g) K1 (L/min) R Qcal (mg/g) K2 (g/mg min) R2

PVA/SBA-15(10%) 35.2 8.31 0.0207 0.722 37.03 0.00574 0.999

PVA/SBA-15(30%) 38.8 6.59 0.0161 0.636 40 0.01201 0.999
PVA//SBA-15(50%) 30.8 5.83 0.0230 0.509 31.25 0.00984 0.998
PVA/SBA-15(75%) 26.79 4.53 0.0138 0.499 27.02 0.01256 0.999
J Mater Sci

100 80
PVA/SBA-15(10%)
70 PVA/SBA-15(30%)
80 PVA/SBA-15(50%)
60 PVA/SBA-15(75%)

60 50
Qads (%)

Qads (mg/g)
40
40
30
PVA/SBA-15(10%)
20 PVA/SBA-15(30%) 20
PVA/SBA-15(50%)
PVA/SBA-15(75%) 10
0
10 20 30 40 50 0 10 20 30 40 50 60 70 80 90
Mass of adsorbent (mg) Ci (mg/L)

Figure 8 Effect of adsorbent mass on the adsorption capacity of Figure 9 Effect of initial concentration of MB dye on adsorption
MB dye. capacity.

Effect of initial concentration 1,0

PVA/SBA-15(10%)
and adsorption isotherms study PVA/SBA-15(30%)
0,8 PVA/SBA-15(50%)
The adsorption isotherm is a representative charac- PVA/SBA-15(75%)
teristic of the thermodynamic equilibrium between
an adsorbent and an adsorbate. It is very useful for 0,6
Ce/Qe

understanding the adsorption mechanism [22]. In this

study, the effect of initial concentration of MB dye on
0,4
adsorbed quantity (mg/g) was studied in the range
of concentrations between 10 and 80 mg/L. We also
note that the adsorbed quantity of MB dye increases 0,2
with increase in the initial concentration of the
adsorbent, until saturation of all adsorption sites.
This shows that MB dye is adsorbed homogeneously. 0,0
0 5 10 15 20 25 30 35 40
It is also observed that the composite PVA/SBA-
Ce (mg/L)
15(30%) has a high adsorption capacity compared to
other materials (see Fig. 9). Figure 10 Linear modeling by the Langmuir model.
The linearization model of Langmuir and Fre-
undlich is presented in Figs. 10 and 11, and the dif- are homogeneous in terms of energy and a mono-
ferent parameters of the both models are shown in layer adsorption of MB dye on composites PVA/
Table 3. Judging by the value of the correlation SBA-15 [22]. These results confirm that the Langmuir
coefficient (R2 [ 0.931), the adsorption isotherms are model better describes the adsorption process of MB
simulated very correctly by the Langmuir linear dye.
model, confirming monolayer and homogeneous Table 4 shows a comparative study of different
adsorption, and the nf value (case of Freundlich materials toward adsorption of MB dye. It is clearly
model) is greater than 1 showing that the physical shown that the structure of the materials plays a very
adsorption is favorable. Overall, we find that the important role in the adsorption of MB dye; in gen-
Langmuir linear model is the most credible model eral, the mesoporous materials give better results
that better describes these experimental results, with compared to the microporous materials (zeolites),
qmax of 52.63–76.92 mg/g and R2 [ 0.979. The Lang- this is strongly related to the accessibility of dye
muir model shows that the surfaces of the composites inside the pores. We also find that the modification of
 J Mater Sci

2,0 Table 4 Comparison between the adsorption capacities of

PVA/SBA-15(10%) composite and other adsorbents
PVA/SBA-15(30%)
1,8 PVA/SBA-15(50%) Samples q (mg/g) References
PVA/SBA-15(75%)
ZIF-8 11.6–16.6 [47]
1,6 ZIF-67 9.8–12.9 [47]
Log(Qe)

PPy/SBA-15(1%) 58.82 [22]

1,4 SBA-15 38.06 [22]
Natural zeolite 21.78 [48]
Graphene 50 [49]
1,2 Carbon nanotubes 35 [50]
Silica nano-sheets 12.7 [51]
1,0 MMSHNs-3 25 [52]
MCM-41 48 [53]
-1,0 -0,5 0,0 0,5 1,0 1,5
ZFA/HZ 45.1 [54]
PVA/SBA-15(30%) 76.92 Present study
Log(Ce)

Figure 11 Linear modeling by the Freundlich model.

Table 3 Isotherm parameters by the Langmuir and Freundlich Conclusions

models
The mesoporous silica SBA-15 was well synthesized
Adsorbent qmax (mg/g) KL (L/mg) R2
by hydrothermal route and then used for the prepa-
Langmuir ration of composites PVA/SBA-15. This study
PVA/SBA-15(10%) 55.55 0.529 0.996 showed that PVA has a significant influence on the
PVA/SBA-15(30%) 76.92 1.300 0.995 structural, textural and thermal properties of the
PVA/SBA-15(50%) 55 0.1443 0.979 resulting composites. The impregnation of PVA
PVA/SBA-15(75%) 52.63 0.0940 0.902 inside the pores of SBA-15 led to the improvement in
Adsorbent nf KF (L/g) R2 the MB dye adsorption capacity and also the hydro-
philic character due to enrichment of the surface of
Freundlich
SBA-15 by –OH groups. The results showed that
PVA/SBA-15(10%) 3.28 19.76 0.991
PVA/SBA-15(30%) 2.38 32.50 0.951
there is an optimal percentage of PVA leading to
PVA/SBA-15(50%) 2.31 10.25 0.971 better adsorption capacity of MB dye and that
PVA/SBA-15(75%) 2.43 2.16 0.931 beyond certain percentages of PVA, the adsorption
capacity decreases due to pore blocking. The kinetics
study revealed that the adsorption process of
methylene blue on all materials was described by a
the surface of the mesoporous silica gives better pseudo-second-order process. The dye adsorption
results compared to the parent material SBA-15; this isotherms on composite materials (PVA/SBA-15)
is probably due to the modification of charge state of were satisfactorily described by the Langmuir model.
the surface and the increase of the interactions The electrostatic interaction was considered the main
between the polymer functional groups and the MB mechanism for the adsorption of the MB dye on
dye. composite PVA/SBA-15. It is very interesting to test
This material was reused for several cycles for the performance of these solids for the adsorption of
adsorption of MB dye. The results showed that its other pollutants such as transition metals, phenol and
adsorption capacity decreased slightly and its its derivatives, anionic dyes and also adsorption of
removal efficiency was appreciable even after five gas (VOCs, CO2, etc.). It is also interesting to immo-
reuses confirming its stability (see Fig. 2S). bilize other polymers on the mesoporous silica to test
their adsorption affinities via cationic and anionic
dyes.
J Mater Sci

Compliance with ethical standards [11] Kessouri A, Boukoussa B, Bengueddach A, Hamacha R

(2018) Synthesis of iron-MFI zeolite and its photocatalytic
Conflict of interest The authors declare that they application for hydroxylation of phenol. Res Chem Intermed
have no conflict of interest. 44:2475–2487
[12] Bellatreche S, Hasnaoui A, Boukoussa B, Garcı́a-Aguilar J,
Electronic supplementary material: The online Berenguer-Murcia Á, Cazorla-Amoros D, Bengueddach A
version of this article (https://doi.org/10.1007/s108 (2016) Structural and textural features of TiO2/SAPO-34
53-019-03415-w) contains supplementary material, nanocomposite prepared by the sol–gel method. Res Chem
which is available to authorized users. Intermed 42:8039–8053
[13] Hameed BB, Ismail ZZ (2018) Decolorization, biodegrada-
tion and detoxification of reactive red azo dye using non-
References adapted immobilized mixed cells. Biochem Eng J 137:71–77
[14] Li J, Gong JL, Zeng GM, Zhang P, Song B, Cao WC, Liu
[1] Schweitzer L, Noblet J (2018) Chapter 3.6—Water con-
HY, Huan SY (2018) Zirconium-based metal organic
tamination and pollution. Green Chem 1:261–290. https://d
frameworks loaded on polyurethane foam membrane for
oi.org/10.1016/B978-0-12-809270-5.00011-X
simultaneous removal of dyes with different charges. J Col-
[2] Vikrant K, Giri BS, Raza N, Roy K, Kim KH, Nath Rai B,
loid Interface Sci 527:267–279
Singh RS (2018) Recent advancements in bioremediation of
[15] Hassani KE, Kalnina D, Turks M, Beakou BH, Anouar A
dye: current status and challenges. Bioresour Technol
(2019) Enhanced degradation of an azo dye by catalytic
253:355–367
ozonation over Ni-containing layered double hydroxide
[3] Rawat D, Mishra V, Sharma RS (2016) Detoxification of azo
nanocatalyst. Sep Purif Technol 210:764–774
dyes in the context of environmental processes. Chemo-
[16] Nidheesh PV, Zhou M, Oturan MA (2018) An overview on
sphere 155:591–605
the removal of synthetic dyes from water by electrochemical
[4] Wainwright M (2017) The problem with dyes in infection
advanced oxidation processes. Chemosphere 197:210–227
control. Dyes Pigm 146:402–407
[17] Hassan MM, Carr CM (2018) A critical review on recent
[5] Jiao J, Wang J, Li M, Li J, Li Q, Quan Q, Chen J (2016)
advancements of the removal of reactive dyes from dyehouse
Simultaneous determination of three azo dyes in food pro-
effluent by ion-exchange adsorbents. Chemosphere
duct by ion mobility spectrometry. J Chromatogr B
209:201–219
1025:105–109
[18] Hussain I, Li Y, Qi J, Li J, Wang L (2018) Nitrogen-enriched
[6] Zhu J, Deng C, Jiang H, Zheng Z, Gong R, Bi Y, Zhang L,
carbon sheet for Methyl blue dye adsorption. J Environ
Lin R (2016) The impact of fluorescent dyes on the perfor-
Manag 215:123–131
mances of polystyrene-based plastic scintillators. Nucl
[19] Hamza W, Dammak N, Bel Hadjltaief H, Eloussaief M,
Instrum Methods Phys Res Sect A 835:136–141
Benzina M (2018) Sono-assisted adsorption of cristal violet
[7] Burnier P, Niddam J, Bosc R, Hersant B, Meningaud JP
dye onto Tunisian smectite clay: characterization, kinetics
(2017) Indocyanine green applications in plastic surgery: a
and adsorption isotherms. Ecotoxicol Environ Saf
review of the literature. J Plast Reconstr Aesthet Surg
163:365–371
70:814–827
[20] Fardjaoui NEH, El Berrichi FZ, Ayari F (2017) Kaolin-is-
[8] Shindy HA (2017) Fundamentals in the chemistry of cyanine
sued zeolite A as efficient adsorbent for bezanyl yellow and
dyes: a review. Dyes Pigment 145:505–513
nylomine green anionic dyes. Microporous Mesoporous
[9] Ritter EE, Dickinson ME, Harron JP, Lunderberg DM,
Mater 243:91–101
DeYoung PA, Robel AE, Field JA, Peaslee GF (2017) PIGE
[21] Boukoussa B, Hamacha R, Morsli A, Bengueddach A (2017)
as a screening tool for per-and polyfluorinated substances in
Adsorption of yellow dye on calcined or uncalcined Al-
papers and textiles. Nucl Instrum Methods Phys Res Sect B
MCM-41 mesoporous materials. Arab J Chem 10:S2160–
407:47–54
S2169
[10] Hamoud HI, Finqueneisel G, Azambre B (2017) Removal of
[22] Boukoussa B, Hakiki A, Moulai S, Chikh K, Kherroub DE,
binary dyes mixtures with opposite and similar charges by
Bouhadjar L, Guedal D, Messaoudi K, Mokhtar F, Hamacha
adsorption, coagulation/flocculation and catalytic oxidation
R (2018) Adsorption behaviors of cationic and anionic dyes
in the presence of CeO2/H2O2 Fenton-like system. J Environ
from aqueous solution on nanocomposite polypyrrole/SBA-
Manag 195:195–207
15. J Mater Sci 53:7372–7386. https://doi.org/10.1007/s108
53-018-2060-7

[23] Benhamou A, Baudu M, Derriche Z, Basly JP (2009)
Aqueous heavy metals removal on amine-functionalized Si-
MCM-41 and Si-MCM-48. J Hazard Mater 171:1001–1008
[24] Benhamou A, Basly JP, Baudu M, Derriche Z, Hamacha R
(2013) Amino-functionalized MCM-41 and MCM-48 for the
removal of chromate and arsenate. J Colloid Interface Sci
404:135–139
[25] Boukoussa B, Hakiki A, Nunes-Beltrao AP, Hamacha R,
Azzouz A (2018) Assessment of the intrinsic interactions of
nanocomposite polyaniline/SBA-15 with carbon dioxide:
correlation between the hydrophilic character and surface
basicity. J CO2 Util 26:171–178
[26] Boukoussa B, Zeghada S, Bentabed Ababsa G, Hamacha R,
Derdour A, Bengueddach A, Mongin F (2015) Catalytic
behavior of surfactant-containing-MCM-41 mesoporous
materials for cycloaddition of 4-nitrophenyl azide. Appl
Catal A 489:131–139
[27] Ouargli-Saker R, Bouazizi N, Boukoussa B, Barrimo D,
Nunes-Beltrao AP, Azzouz A (2017) Metal-loaded SBA-16-
like silica—Correlation between basicity and affinity
towards hydrogen. Appl Surf Sci 411:476–486
[28] Ghomari K, Boukoussa B, Hamacha R, Bengueddach A,
Roy R, Azzouz A (2017) Preparation of dendrimer polyol/
mesoporous silica nanocomposite for reversible CO2
adsorption: effect of pore size and polyol content. Sep Sci
Technol 52:2421–2428
[29] Boukoussa B, Kibou Z, Abid Z, Ouargli R, Choukchou-
Braham N, Villemin D, Bengueddach A, Hamacha R (2018)
Key factor affecting the basicity of mesoporous silicas
MCM-41: effect of surfactant extraction time and Si/Al ratio.
Chem Pap 72:289–299
[30] Sekkiou H, Boukoussa B, Ghezini R, Khenchoul Z, Ouali A,
Hamacha R, Bengueddach A (2016) Enhanced hydrogen
storage capacity of copper containing mesoporous silicas
prepared using different methods. Mater Res Express
3:085501
[31] Hakiki A, Boukoussa B, Habib Zahmani H, Hamacha R,
Hadj Abdelkader NEH, Bekkar F, Bettahar F, Nunes-Beltrao
AP, Hacini S, Bengueddach A, Azzouz A (2018) Synthesis
and characterization of mesoporous silica SBA-15 func-
tionalized by mono-, di-, and tri-amine and its catalytic
behavior towards Michael addition. Mater Chem Phys
212:415–425
[32] Wang J, Ge H, Bao W (2015) Synthesis and characteristics
of SBA-15 with thick pore wall and high hydrothermal
stability. Mater Lett 145:312–315
[33] Peng K, Li X, Liu X, Wang Y (2017) Hydrothermally
stable Nb-SBA-15 catalysts applied in carbohydrate con-
version to 5-hydroxymethyl furfural. Mol Catal 441:72–80
J Mater Sci
[34] Talha Z, Bachir C, Ziri S, Bellahouel S, Bengueddach A,
Villièras F, Pelletier M, Weidler PG, Hamacha R (2017) Al-
Rich ordered mesoporous silica SBA-15 materials: synthesis,
surface characterization and acid properties. Catal Lett
147:2116–2126
[35] Arica TA, Ayas E, Yakup Arica M (2017) Magnetic MCM-
41 silica particles grafted with poly(glycidylmethacrylate)
brush: modification and application for removal of direct
dyes. Microporous Mesoporous Mater 243:164–175
[36] Kumar Mahto T, Chandra S, Haldar C, Kumar Sahu S (2015)
Kinetic and thermodynamic study of polyaniline function-
alized magnetic mesoporous silica for magnetic field guided
dye adsorption. RSC Adv 5:47909–47919
[37] Gao Q, Zhu H, Luo WJ, Wang S, Zhou CG (2014) Prepa-
ration, characterization, and adsorption evaluation of chi-
tosan-functionalized mesoporous composites. Microporous
Mesoporous Mater 193:15–26
[38] Mirzaie M, Rashidi A, Tayebi HA, Yazdanshenas ME (2017)
Removal of anionic dye from aqueous media by adsorption
onto SBA-15/polyamidoamine dendrimer hybrid: adsorption
equilibrium and kinetics. J Chem Eng Data 62:1365–1376
[39] Hadizade G, Binaeian E, Sarmasti Emami MR (2017)
Preparation and characterization of hexagonal mesoporous
silica/polyacrylamide nanocomposite capsule (PAM-HMS)
for dye removal from aqueous solutions. J Mol Liq
238:499–507
[40] Sharma A, Dubey A (2017) Surface modified mesoporous
silica polymer nanocomposites for adsorption of dyes from
aqueous solution. J Porous Mater 24:429–435
[41] Zhao D, Huo Q, Feng J, Chmelka BF, Stucky GD (1998)
Nonionic triblock and star diblock copolymer and oligomeric
surfactant syntheses of highly ordered, hydrothermally
stable, mesoporous silica structures. J Am Chem Soc
120:6024–6036
[42] Qi X, Hu X, Wei W, Yu H, Li J, Zhang J, Dong W (2015)
Investigation of salecan/poly(vinyl alcohol) hydrogels pre-
pared by freeze/thaw method. Carbohyd Polym 118:60–69
[43] Wang LY, Wang MJ (2016) Removal of heavy metal ions by
poly(vinyl alcohol) and carboxymethyl cellulose composite
hydrogels prepared by a freeze–thaw method. ACS Sustain
Chem Eng 4:2830–2837
[44] Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA,
Rouquerol J, Siemieniewska T (1985) Reporting
physisorption data for gas/solid systems with special refer-
ence to the determination of surface area and porosity. Pure
Appl Chem 57:603–619
[45] Abd El-Hafiz DR, Riad M, Mikhail S (2015) Nano-struc-
tured Mn–Al and Co–Al oxide materials for catalytic ethanol
conversion. J Nanostruct Chem 5:393–403
J Mater Sci
[46] Parlayici S, Eskizeybek V, Avcı A, Pehlivan E (2015)
Removal of chromium (VI) using activated carbon-sup-
ported-functionalized carbon nanotubes. J Nanostruct Chem
5:255–263
[47] Li Y, Zhou K, He M, Yao J (2016) Synthesis of ZIF-8 and
ZIF-67 using mixed-base and their dye adsorption. Micro-
porous Mesoporous Mater 234:287–292
[48] Wang S, Zhu ZH (2006) Characterisation and environmental
application of an Australian natural zeolite for basic dye
removal from aqueous solution. J Hazard Mater
136:946–952
[49] Wu T, Cai X, Tan S, Li H, Liu J, Yang W (2011) Adsorption
characteristics of acrylonitrile, P-Toluenesulfonic acid,
1-naphthalenesulfonic acid and methyl blue on graphene in
aqueous solutions. Chem Eng J 173:144–149
[50] Yao Y, Xu F, Chen M, Xu Z, Zhu Z (2010) Adsorption
behavior of methylene blue on carbon nanotubes. Biores
Technol 101:3040–3046
[51] Zhao M, Tang Z, Liu P (2008) Removal of methylene blue
from aqueous solution with silica nano-sheets derived from
vermiculite. J Hazard Mater 158:43–51
[52] Liu J, Hartono SB, Jin YG, Li Z, Lu GQM, Qiao SZ (2010)
A facile vesicle template route to multi-shelled mesoporous
silica hollow nanospheres. J Mater Chem 20:4595–4601
[53] Monash P, Pugazhenthi G (2010) Investigation of equilib-
rium and kinetic parameters of methylene blue adsorption
onto MCM-41. Korean J Chem Eng 27:1184–1191
[54] Lin LD, Lin Y, Li CJ, Wu DY, Kong HN (2016) Synthesis of
zeolite/hydrous metal oxide composites from coal fly ash as
efficient adsorbents for removal of methylene blue from
water. Int J Miner Process 148:32–40
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