Applied Clay Science 135 (2017) 35–44

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Applied Clay Science

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

Research paper

Adsorption study of reactive dyes onto porous clay heterostructures

J.E. Aguiar a, J.A. Cecilia b, P.A.S. Tavares a, D.C.S. Azevedo a, E. Rodríguez Castellón b,
S.M.P. Lucena a, I.J. Silva Junior a,⁎
a
Departamento de Engenharia Química, Universidade Federal do Ceará, Grupo de Pesquisa em Separações por Adsorção, GPSA, Campus do Pici, Bloco 709, CEP 60455-760 Fortaleza, CE, Brazil
b
Departamento de Química Inorgánica, Cristalografia y Mineralogía, Faculdad de Ciencias, Universidad de Málaga, 29071 Málaga, Spain

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

Article history: The present research evaluates the adsorption of reactive dyes, Remazol Violet 5R (RV5R) and Acid Blue 25
Received 13 June 2016 (AB25), using Porous Clay Heterostructures (PCHs) prepared from natural bentonite. Natural bentonite, PCH
Received in revised form 1 September 2016 with silica pillars (Si-PCH) and PCH with silica-zirconia (SiZr-PCH) were characterized by elemental analysis,
Accepted 2 September 2016
XRD, N2 adsorption-desorption at −196 °C, FT-IR, TG and XPS. The adsorption experiments were carried out in
Available online 16 September 2016
a stirred tank in order to evaluate the effect of pH, contact time and initial concentration. The adsorption iso-
Keywords:
therms were well fitted by Langmuir (L), Langmuir-Freundlich (LF) and Redlich Peterson (RP) models. The equi-
Dye librium data were described using the Langmuir-Freundlich model for both dyes and both materials, obtaining a
Clay maximum adsorption capacity of 209.9 mg g−1 and 265.9 mg g−1 for AB25 using Si-PCH and SiZr-PCH, respec-
Porous clay heterostructure tively. In the case of RV5R, the maximum adsorption capacity was 127.07 mg g−1 and 185.7 mg g−1 for Si-PCH
Adsorption and SiZr-PCH, respectively. The adsorption process takes place by electrostatic interactions between the silanol
groups of the PCHs with functional groups of the dyes, such as amine or hydroxyl. From the obtained results, it
can be concluded that PCHs showed to be a promising material for the adsorption of dye.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction separation, flocculation-coagulation, ozonation, oxidation, sedimenta-

In the last decades, the widespread contamination of groundwater
and soils as a consequence of synthetic organic chemicals, e.g. dyes com-
ing from the textile and related industries, has been considered an im-
portant issue worldwide (İyim and Güçlü, 2009). Dyes can be
classified as a function of the charge in anionic, cationic and non-ionic
compounds. Among them, anionic dyes are widely used as colorant in
the textile industry in wool, silk, acrylic, leather or nylon. These dyes
are formed by aromatic compounds with nitrogen or sulfur centers
leading to an obvious coloration. Nonetheless, these compounds are
harmful and potential human carcinogen, even at low concentrations.
The use of colorants in the textural industry generates effluents highly
colored which provoke numerous operational problems in municipal
wastewater treatment due to high biological oxygen demand (BOD)
and high chemical oxygen demand (COD), high conductivity and alka-
line nature of these effluents (Ozturk et al., 2009). In addition, the pres-
ence of metal together with the dyes in the wastewater can provoke a
microbial inhibition.
The treatment of the wastewaters depends on the physicochemical
properties of the dye as well as the treatment technology selected
(Abbassi et al., 2013). Several methodologies have been proposed to di-
minish the content of colorant of wastewater such as membrane
⁎ Corresponding author.
E-mail address: ivanildo@gpsa.ufc.br (I.J. Silva).
tion, reverse osmosis, flotation, precipitation, and aerobic or anaerobic
treatment (Leodopoulos et al., 2014; Yagub et al., 2014). However the
most of them are infeasible due to their high cost or low efficiency.
The adsorption is a usual method to the treatment of wastewater for
dye removal due to the availability of adsorbents, its simplicity in oper-
ation and high efficiency (Almeida et al., 2009).
Actually, the dyes adsorption is focused in the use of natural solid
materials, which can be able to remove pollutants from contaminated
water with low-cost. In this sense, it has been proposed clay minerals,
siliceous materials or zeolites as natural absorbents by physical and/or
chemical interactions with the dyes. Among them, clay minerals, and
specially bentonites, have shown to be interesting adsorbents with
low cost materials, large availability, thermal and chemical stability in
a wide range of pH and interesting properties in the adsorption field
(Abbassi et al., 2013). Bentonite is formed mainly by montmorillonite,
which displays a lamellar structure where Si4+ species are partially re-
placed by Al3+ species in the tetrahedral positions and Al3+ species are
partially substituted by Mg2+ or Fe2+ species in octahedral positions.
This fact gives rise to the development of negative charges in the layers,
which are balanced by the presence of Na+, K+ or Mg2+ cations strong-
ly hydrated located in the interlayered space (Brindley, 1980). Montmo-
rillonite has been treated or modified with several methods to improve
its physicochemical properties. Thus, it has been proposed the acid
treatment to improve the specific surface area of this smectite
(Al-Khatib et al., 2012; Pentrák et al., 2012; Toor et al., 2015) or the

http://dx.doi.org/10.1016/j.clay.2016.09.001
0169-1317/© 2016 Elsevier B.V. All rights reserved.
36 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44

incorporation of bulky cations in the interlayered spacing to favor the

electrostatic interaction between the bulky cations and the dyes (Tong
et al., 2010; Kıranşan et al., 2014; Anirudhan and Ramachandran,
2015; Grundgeiger et al., 2015). However, the acid treatment leads to
the partial digestion of the clay together with the loss of the silanol
groups, which causes a decrease of available active sites that should in-
teract with the dye. With regard to the intercalation with bulky cations
located in the interlayer spacing, the presence of these bulky cations
provokes a drastic decline of the available specific surface area.
In order to improve the adsorption capacity of the montmorillonite,
several methods, such as the synthesis of pillared interlayered clays
(PILCs) with the use of polyoxocations (Vaccari, 1999), have been pro-
posed. In 1995, Galarneau et al. described the synthesis of a porous ma-
terial, denoted as PCH, from cationic exchange of the cations located in
the interlayer spacing by a bulky cation, which produces the expansion
of the interlayer spacing, and subsequent formation of silica pillars in-
tercalated between two adjacent layers (Galarneau et al., 1995). Recent-
ly (Cecilia et al., 2013) have proposed a new method of synthesis with
the incorporation of zirconium in the pillars. This method allows the
control of the pore size leading to materials with high surface area
(N 600 m2 g−1) with high micro- and mesoporosity. The chemical be-
havior of the PCH can be modified by the insertion of heteroatoms
such as Al, Zr or Ti in the pillars, which produces an increasing of the
acidity and provides to the material a higher thermal and mechanical
stability (Cecilia et al., 2013). In addition, these materials display higher
hydrophilicity than the natural clays, which improves the performance Fig. 1. Chemical structure of the Remazol Violet 5R-RV5R (a) and Acid Blue 25-AB25 (b).
in the adsorption and catalysis, thereby generating their extensive use
in the removal of different compounds (Roca Jalil et al., 2013).
The present research describes the synthesis and characterization of hexadecylamine (90%, Aldrich), used as co-surfactant, was dissolved in
porous clay heterostructures, which contains silica or silica-zirconium 25 mL of n-propanol solution, added to the mother solution and stirred
pillars, from a natural bentonite. These materials have been evaluated for 24 h. The Si-pillars located between adjacent layers of montmoril-
as adsorbents in the removing azo dyes in aqueous solutions in batch lonite were formed by the incorporation of a solution of 11.1 mL
adsorption experiments. tetraethylorthosilicate (TEOS) (98, Aldrich), as silicon source. The for-
mation of Si\\Zr pillars with a molar ratio Si/Zr = 5 were generated
2. Material and methods by the addition of a solution of 9.4 mL of TEOS and 2.25 mL of zirconium
propoxide (70%, Aldrich) dissolved in both cases in n-propanol
2.1. Dyes (50 vol.%). The obtained gel was stirred during 72 h and then was fil-
tered and washed with water-ethanol and dried at 60 °C in air for
Dye Remazol Violet 5R (trisodium; (3Z)-5-acetamido-3-[[2-hy- 12 h. Finally, the surfactant was removed by the calcination at 550 °C
droxy-5-(2-sulfonatooxyethylsulfonyl) phenyl] hydrazinylidene]-4-ox- with a rate of 1 °C min−1 during 6 h. Elemental analysis CNH were car-
onaphthalene-2,7-disulfonate - C20H16N3Na3O15S4) with molar mass of ried out to ensure the complete combustion of the surfactant.
735.6 g mol− 1, UV–visible λmax = 562 nm. Dye Acid Blue 25 (2-
Anthracenesulfonic acid, 1-amino-9,10-dihydro-9,10-dioxo-4-
(phenylamino), monosodium salt - C20H13O5N2SNa) with molar mass 2.3. Characterizations of porous clay heterostructures
of 416.4 g mol−1, UV–visible λmax = 605 nm. The dyes used were ob-
tained from Sigma-Aldrich with a high degree of purity. The structures The purified montmorillonite was examined by scanning electron
of dyes are shows in Fig. 1. Remazol Violet 5R is formed by an aromatic microscope (SEM) using a JEOL SM-6490 LV combined with X-ray ener-
framework with aryl, amide and sulfonic groups, while Acid Blue 25 is gy dispersive spectroscopy (EDX). The samples were gold sputtered in
also formed by an aromatic structure with amine and sulfonic groups. order to avoid charging of the surface. Elemental composition of the
bentonite was achieved by the average of EDX chemical analyses of 40
2.2. Porous clay heterostructures synthesis grains.
X-ray powder patterns for the samples were collected on a X'Pert
The synthesis of the porous clay heterostructures (PCHs) were car- Pro MPD automated diffractometer (PANalytical B.V.) equipped with a
ried out following the procedure described by (Cecilia et al., 2013) in a Ge (111) primary monochromator (strictly monochromatic CuKα1 ra-
previous research. diation) and an X'Celerator detector with a step size of 0.017°. The pow-
The starting bentonite was supplied by Minas de Gador S.A. from “Si- der patterns were recorded between 10° and 70° in 2θ with a total
erra de Gador” (Spain). The raw bentonite was purity to obtain the measuring time of 30 min. Low angle measurements were obtained
montmorillonite fraction by a sedimentation process. Later, the mont- with the same configuration maintaining the divergence and anti-diver-
morillonite fraction was treated with a NaCl solution (1 M) for 24 h to gence aperture at 1/16° and with Soller of 0.02 rad. Measurements were
generate the homoionic Na-montmorillonite. carried out between 0.5–10° in 2θ with a step size of 0.017°.
In a typical PCH synthesis, 2.5 g of Na-montmorillonite was treated The textural parameters (SBET, VP and dP) were evaluated from the
with 9 g of hexadecyltrimethylammonium bromide (HDTMBr) (Al- nitrogen adsorption-desorption isotherms at − 196 °C as determined
drich) in 100 mL of n-propanol (99.9%, VWR). After 3 days under stir- by an automatic ASAP 2020 system from Micromeritics. Prior to the
ring, the solution was filtered and was washed with distilled water to measurements, samples were outgassed at 200 °C and 10−4 mbar over-
remove the non-intercalated HDTMBr. The solid was redissolved in night. Surface areas were determined by using the Brunauer–Emmett–
250 mL of water for 24 h. After this time, a solution of 0.9 g of Teller (BET) equation and a nitrogen molecule cross section of 16.2 Å2.
 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44 37

The total pore volume was calculated from the adsorption isotherm at P/
P0 = 0.996.
Elemental chemical analysis, using a LECO CHNS 932 analyzer, were

Intensity (c.p.s.)
performed to determinate the carbon content present after the calcina-
Cristobalite
tion of the template of the PCHs and to evaluate the dyes adsorption ca-
pacity of the adsorbents. The determination of carbon, nitrogen and Calcite
Montmorillonite
sulfur takes place after the combustion of the samples at 1000 °C in Quartz
pure oxygen to form CO2, NO2 and SO2. Plagioclase
DRIFT spectra were collected on a Harrick HVC-DRP cell fitted to a Montmorillonite
Varian 3100 FT-IR spectrophotometer. The interferograms consisted of
200 scans, and the spectra were collected using a KBr spectrum as a
background. About 30 mg of finely ground clay based materials were
placed in the sample holder. The sample was heated under air flow of
60 mL min− 1 at 200 °C (30 min) to remove the physisorbed water 10 20 30 40 50 60
and thereafter the sample was cooled at room temperature and the
spectra was collected. 2θ (°)
Differential Thermal Analysis (DTA) and thermogravimetry (TGA)
data were taken on a Mettler-Toledo (TGA/DSC 1) analyzer from RT in- Fig. 2. XRD pattern of the raw bentonite.
struments (New Castle, DE). The temperature was varied from RT to
1000 °C at a heating rate of 5 °C min−1. Measurements were carried
out on samples in open platinum crucibles under air flow. Adsorption isotherms were fitted by Langmuir, Langmuir-
X-ray photoelectron spectra were collected using a Physical Elec- Freundlich and Redlich Peterson models, as described by Eqs. (2)–(4),
tronics PHI 5700 spectrometer with non-monochromatic Mg Kα radia- respectively:
tion (300 W, 15 kV, and 1253.6 eV) with a multi-channel detector.
Spectra of pelletized samples were recorded in the constant pass energy
mode at 29.35 eV, using a 720 μm diameter analysis area. Charge qmax K L C eq
q¼ ð2Þ
referencing was measured against adventitious carbon (C 1s at 1 þ K L C eq
284.8 eV). A PHI ACCESS ESCA-V6.0 F software package was used for ac-
quisition and data analysis. A Shirley-type background was subtracted
from the signals. Recorded spectra were always fitted using Gaussian–
(a)
Lorentzian curves in order to determine the binding energies of the dif-
ferent element core levels more accurately. The samples was introduced
into the analysis chamber, and directly analyzed without previous
treatment.
Intensity (c.p.s.)

2.4. Adsorption experiments

Bentonite
Several batch experiments were carried out in order to obtain infor-
mation about the effect the pH of medium, contact time and initial dye
concentration. All adsorption experiments were carried out at 22 °C. Si-PCH
After prepare dye stock solutions, adsorption experiments were per-
SiZr-PCH
formed in a rotatory shaker (Tecnal TE-165, Brazil). For this aim,
20 mL of dye solution was added to 50 mL conical tubes containing
0.02 g of PCH. At the end of each experiment, the supernatant was 2 3 4 5 6 7 8
collected and centrifuged for 10 min at 10.000 rpm (refrigerated 2θ (°)
microcentrifuge Cientec CT – 15000R). The dye concentration in the liq-
uid phase (supernatant) was determined by UV–Vis light absorbance at
λ = 562 nm for AB25 and λmax = 605 nm for RV5R (UV–Vis spectro- (b)
photometer Biomate 3, ThermoScientific, USA).
(020)
The adsorption of AB25 and RV5R dyes in single system were studied (110)
in pH range 2 to 12 taking account the equilibrium conditions, i.e. after
Intensity (c.p.s.)

60 min. The pH adjustment of the stock solution was carried out using
HCl or NaOH solutions. For the kinetic adsorption, the samples were col- (130)
lected in the experimental tubes at pre-determined time intervals (5 to (200)

120 min). Adsorption isotherms were determined by the analysis of the

residual dye concentration from aqueous solution at increasing initial (060)
concentrations. For this aim, solutions of different dye initial concentra- SiZr-PCH
tion (25–300 ppm) were evaluated. Dye amount adsorbed in the solid
phase (adsorption capacity – q) was calculated according to Eq. (1):

Si-PCH
Vsol C0 −Ceq
q¼ ð1Þ
mads 10 20 30 40 50 60 70
2θ (°)
where Vsol is the volume solution (mL), C0 is the initial liquid concentra-
tion (mg/mL), Ceq is the equilibrium liquid concentration (mg/mL) and Fig. 3. Low-angle XRD pattern of raw bentonite, Si-PCH and SiZr-PCH (a) and high-angle
mads is the mass adsorbent (g). XRD pattern of Si-PCH and SiZr-PCH (b).
38 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44

Table 1 (a)
Textural properties of natural montmorillonite, Si-PCH and SiZr-PCH.

Samples SBET t-plotMicrop VP VP(Microp)

[m2 g−1] [m2 g−1] [cm3 g−1] [cm3 g−1]

Absorbance (a.u.)
BG 49 18 0.11 0.01
Si-PCH 644 460 0.77 0.28
SiZr-PCH 608 382 0.82 0.21
3740

qmax K LF C eq b
q¼ ð3Þ
1 þ K LF C eq
3635

qmax K RP C eq
q¼ ð4Þ 4000 3800 3600 3400 3200 3000 2800
1 þ K RP C eq β -1
Wavenumber (cm )
where Ceq (mg/mL) is the dye concentration of the aqueous phase in
(b)
equilibrium with adsorbed dye concentration in solid phase – q
(mg g−1), qmax (mg g−1) is the maximum amount adsorbed dye per 1300-1000
gram of adsorbent, KL, KLF and KRP are the binding constants of Langmuir,
946
Langmuir-Freundlich and Redlich-Peterson models. b and β are the ex-

Absorbance (a.u.)
ponents of the Langmuir-Freundlich and Redlich-Peterson that define 1630 800
the heterogeneity of the system so in the case of b and β = 1, the system
is homogeneous and the model is reduced to the Langmuir equation.

466
522
1030
1116 916 623
Quantity Adsorbed (cm g STP)

(a) 800

500 2000 1800 1600 1400 1200 1000 800 600

-1

-1
Wavenumber (cm )
3

400

Fig. 5. FT-IR spectra of raw bentonite (black), Si-PCH (red) and SiZr-PCH (green) in the
300 region 4000–2800 cm−1 (a) and 2000–450 cm−1 (b).

200

100 3. Results and discussion

0 3.1. Structural and textural characterization

0.0 0.2 0.4 0.6 0.8 1.0

Relative Pressure (P/P0) The elemental analysis of the homoionic montmorillonite (Na-
mont) was estimated using EDX chemical analysis by the evaluation of
Differential Pore Volume (cm g )
-1

(b) the average of 40 grains, obtaining the following structural formula:

1.5
3

VI IV
ðNa0:8 ÞðAl3:3 Mg0:5 Fe0:2 Þ ðSi7:7 Al0:3 Þ O20 ðOHÞ4
1.2
where the substitution of silicon by aluminum in the octahedral posi-
0.9 tions (VI) and the substitution of aluminum by iron and magnesium in
the tetrahedral positions (IV) are balanced with the presence of sodium
0.6 in the interlayer spacing.
According to the Schultz classification (Schultz, 1969), the obtaining
0.3
formula represents a Wyoming-type bentonite, where the layer charge
is lower than 0.85 electron charges per unit cell (e−/u.c.). As previous
reported, the XRD pattern of the raw bentonite reveals that montmoril-
0.0
lonite is the main mineralogical phase. In addition, it is noticeable the
10 100 1000 presence of minor amounts of plagioclase, calcite, cristobalite and
Pore Width (Å) quartz (Zent et al., 2001; Cecilia et al., 2013) (Fig. 2).
Low-angle diffractograms of the Si-PCH and SiZr-PCH (Fig. 3a) reveal
Fig. 4. N2 isotherms at −196 °C: (a) raw bentonite (black), Si-PCH (red) and SiZr-PCH the existence of a broad peak located about 2θ = 2°, assigned to the
(green). (b) Pore size distribution of raw bentonite, Si-PCH and SiZr-PCH. presence of d001 reflexion line, confirming the generation of the
 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44 39

30
small amount of zirconium into the pillars provokes a slight shrinkage
25
in the hysteresis loop due to silicon and zirconium alcoxides have differ-
ent hydrolysis rate, leading to the formation of blind cylindrical, cone-
Mass Loss (%)

20
15
10
5
0 of Zr species in the pillars causes a delamination of the material
0 100 200 300 400 500 600 700 800 900 1000
Temperature (˚C)
Fig. 6. Thermogravimetric analysis of the raw bentonite (black), Si-PCH (red) and SiZr-
PCH (green).
expanded porous clay structure where the silica or silica-zirconia pillars
separate two adjacent sheets (Galarneau et al., 1995) in comparison
with the starting bentonite. In addition, the XRD patterns reflect that
the incorporation of zirconium in the pillars produces a decrease of
the intensity of the diffraction peak located at low-angle, suggesting a
slight delamination of the PCH framework and leading to a more disor-
dered structure denoted as “house of cards” (Occelli, 1988).
With regard to the high-angle diffractograms (Fig. 3b), it is notewor-
thy that the basal diffraction lines of both Si-PCH and SiZr-PCH disap-
pear. The non-basal diffraction peaks (020, 110, 200, 060) are
detected, although their intensities decrease in comparison with the
raw bentonite, which confirms the structural modification along c-axis
and a random displacement in the a- and b-axis, corroborating the for-
mation of delaminated framework in all cases.
N2 adsorption-desorption isotherms at −196 °C were carried out to
evaluate the textural properties of the raw bentonite and PCHs (Table 1
and Fig. 4a). Taking account that the specific surface area of the raw ben-
tonite is only of 49 m2 g−1, both Si-PCH and SiZr-PCH display a higher
SBET, 644 m2 g−1 for the Si-PCH and 608 m2 g−1 for the SiZr-PCH, re-
spectively. This increase confirms the incorporation of pillars between
the 2:1 layers of bentonite leading to a well-defined porous framework
which displays micro- meso- and macroporosity in its structure, as re-
veals the isotherms of both PCHs. According to the IUPAC classification
(Sing, 1985), and refined by Rouquerol et al. (2014), both PCHs show
a combination of type I and type IIb isotherms which are associated to
the presence of microporosity and the latter with monolayer-multilayer
adsorption on an open and stable external surface of a powder with
macroporosity. These isotherms are typical of aggregates of plate-like
particles, which possess non-rigid slit-shaped pores. In addition, both
PCHs display a narrow H3-type hysteresis loops with no indication of
a plateau at high P/P0, which is attributed to the presence of agglomer-
ates of particles forming slit shaped pores (plates or edged particles like
cubes) (Robens, 1999; Rouquerol et al., 2014). The incorporation of a
shaped and wedge-shaped pores (Sing, 1985) which have been de-
scribed in a “house of cards” structures (Occelli, 1988). In the present
study, the pore width distribution of Si-PCH and SiZr-PCH (Fig. 4b)
displayed similar pattern for both adsorbents. In both case, it is note-
worthy the coexistence of micro- and mesoporosity by the insertion of
pillars between adjacent layers and macroporosity due to the interpar-
ticle voids. It has been reported in the literature that the incorporation
(Cecilia et al., 2013); however the presence of pillars with a molar
ratio Si/Zr = 5 seems maintain the same pore size distribution.
Fig. 5a shows the \\OH stretching region of FTIR spectra between
4000 and 2800 cm−1. The raw bentonite displays a set of overlapped
bands between 3760 and 3525 cm− 1, with a maximum about
3635 cm− 1, which is assigned to the stretching modes of the \\OH
groups located inside the 2:1 layers (Zviagina et al., 2004). The forma-
tion of a pillared framework, using silica or silica-zirconia pillars, leads
to the arising of a new band located about 3740 cm−1, which is attribut-
ed to the stretching vibration of the silanol groups (Si\\OH) located be-
tween two adjacent layers (Vilarrasa et al., 2014). The band with a
maximum at 3635 cm−1 is attributed to the montmorillonite that re-
mains unaltered.
According to previous assignation bands (Fig. 5b) (Farmer, 1998;
Madejová, 2003) for the OH-groups for dioctahedral smectites, the
raw bentonite exhibits a complex band with a maximum located
about 1030 cm−1 and a shoulder at 1116 cm−1 assigned to the symmet-
ric stretching vibration mode of Si\\O\\Si groups. The band located
about 916 cm−1 is attributed to the bending vibration mode of
Al\\Al\\OH. The band located about 800 cm−1 is assigned to symmetric
stretching mode νs (Si\\O\\Si). The band located about 623 cm−1 is as-
cribed to the Al\\O and Si\\O out-of-plane vibrations, while the bands
located at 466 and 522 cm− 1 is assigned to Al\\O\\Si and Si\\O\\Si
bending vibration. With regard to the region between 2000 and
500 cm−1 of the PCHs, both Si-PCH and SiZr-PCH exhibit a broader ad-
sorption band 1300–1000 cm−1 in comparison to the raw bentonite.
This fact is attributed to the formation of SiO2 or SiO2\\ZrO2 species as
pillars between adjancent layers of montmorillonite (Pinto et al.,
2014). The band located between 975–930 cm− 1 is attributed to the
dangling Si-Od due to Si\\OH and Si\\O (Chmel et al., 1990) and the
band located at 800 cm−1 (Vilarrasa et al., 2014), is assigned to symmet-
ric stretching mode, being more evident for both PCHs and mainly for
Si-PCH due to this adsorbent has a higher silica content. Finally, the
band located about 1630 cm−1 is attributed to bending mode of water
ν2 (H\\O\\H) (Vilarrasa et al., 2014).
The thermogravimetric analysis of the starting bentonite and both
PCH are shown in Fig. 6. The TG analysis reveals two mass losses. This
first one, between 30 and 150 °C, is associated to the progressive loss
of water molecules adsorbed on the surface of the adsorbent. This pro-
cess is more evident for the starting material, while both PCHs contain
a lower amount of water on the surface of the material. This fact can

Table 2
Binding energies of starting montmorillonite, Si-PCH and SiZr-PCH before and after the adsorption process.

Sample Si O Al Fe Ca Mg Na Zr S N
2p 1s 2p 2p 2p 2p 1s 3d 2p 1s

BG 103.7 531.9 74.6 712.6 347.6 49.9 1072.4 – – –

BG-AA25 102.7 531.9 74.6 712.6 347.6 49.6 1072.3 – 168.3 400.3
BG-RV5R 102.8 532.0 74.7 712.4 347.4 48.9 1072.7 – 168.4 401.0
Si-PCH 103.6 532.8 75.1 712.3 – 49.8 – – – –
Si-PCH-AA25 103.4 532.8 74.9 712.3 – 49.8 – – 168.5 400.9
Si_PCH-RV5R 103.3 532.7 74.6 712.3 – 49.7 – 168.3 401.0
SiZr-PCH 103.1 532.8 75.2 712.4 – 49.6 – 183.1 – –
SiZr-PCH-AA25 103.5 532.4 74.8 712.1 – 49.7 – 182.7 168.4 400.8
SiZr-PCH-RV5R 103.3 532.3 74.6 712.2 – 49.7 – 182.8 168.3 401.3
40 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44

Table 3
Atomic concentrations of starting montmorillonite, Si-PCH and SiZr-PCH before and after the adsorption process.

Sample C Si O Al Fe Ca Mg Na Zr S N
1s 2p 1s 2p 2p 2p 2p 1s 3d 2p 1s

BG 11.26 19.53 57.22 8.74 0.51 0.35 1.38 1.01 – – –

BG-AA25 10.99 19.60 56.52 8.93 0.47 0.19 1.81 0.50 – 0.46 0.59
BG-RV5R 10.22 20.20 56.20 9.53 0.39 0.20 1.71 0.40 – 0.43 0.41
Si-PCH 6.68 30.31 60.74 1.83 0.21 – 0.23 – – – –
Si-PCH-AA25 6.60 30.25 60.30 1.63 0.16 – 0.17 – – 0.58 0.71
Si_PCH-RV5R 6.27 30.09 60.63 1.55 0.18 – 0.38 – – 0.46 0.58
SiZr-PCH 10.67 24.47 58.11 2.27 0.22 – 0.58 – 3.68 – –
SiZr-PCH-AA25 10.27 24.06 58.12 2.16 0.21 – 0.54 – 3.37 0.56 0.81
SiZr-PCH-RV5R 9.89 24.44 58.64 1.96 0.16 – 0.39 – 3.59 0.38 0.60

be attributed to the higher amount of\\OH available of the starting ma-
terial, as was shown in the FT-IR spectra (Fig. 5a), which interacts with
water molecules. The second mass loss, located between 400 and 750 °
C, corresponds to the dehydroxylation of structural\\OH groups located
between the tetrahedral sheets of 2:1 bentonite layers. This band is only
detectable for the raw bentonite due to the calcination process, required
to remove the organic cation in the synthesis of PCH, is a exothermic
process and removes a higher proportion of the\\OH groups. Neverthe-
less, the FTIR spectra of both PCHs reveal the presence of silanol groups.
In order to analyze the chemical composition of the raw bentonite,
Si-PCH and SiZr-PCH samples on their surface, XPS measurements
were carried out. Tables 2 and 3 compile the binding energies and atom-
ic concentration of the adsorbents.
XPS spectra of the raw bentonite reveals the presence of a band
about 531.9 eV in the O 1s region, a band about 102.8 eV in the Si 2p re-
gion and another band about 74.6 eV in the Al 2p region which are at-
tributed to the presence of silicate species (Barr, 1990). In addition, it
is noticeable the presence of a band located at 49.9 eV in the Mg 2p re-
gion assigned the Mg2+ species in the form of MgO (Briggs and Eds,
1992), which can be located in the interlayer spacing or probably in
the tetrahedral positions. Finally, a band located at 347.6 eV in the Ca
2p region and another one at 1072.4 eV in the Na 1s region have been

(a)
(a) 180
180
12
12 160
160
140 10
140 10
120
120
q (mg g )
q (mg g )

8
-1
-1

pHfinal
pHfinal

100
100
80 6
80 6
60 4
60 4
40
40
2
2 20
20

0 0 0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12

pHinitial pHinitial

(b) (b)
180 160
12 12
160 140

140 10 120 10

120
q (mg g )
-1

8 100 8
q (mg g )

pHfinal
pHfinal
-1

100
80
6 6
80
60
60 4 4
40
40
2 2
20 20

0 0 0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12

pHinitial pHinitial

Fig. 7. Effect of pH [ο] and different between pHINITIAL and pHFINAL [*] in adsorption of RV5R Fig. 8. Effect of pH [ο] and different between pHINITIAL and pHFINAL [*] in adsorption of RV5R
(a) and AB25 (b) on Si-PCH. (a) and AB25 (b) on SiZr-PCH.
 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44 41

identify for the starting material which have been assigned to Ca2+ and
Na+, respectively (Moulder et al., 1992) which are located in the inter-
layer spacing.
The incorporation of the silica or silica-zirconia pillars to obtain the
PCH leads to changes in the atomic concentrations of adsorbents. Firstly,
the bands located in the O 1s region and the Si 2p region suffer a shift at
higher binding energy about 532.8 eV and 103.2 eV, respectively, which
is attributed to the silicon and oxygen species in the form of silica due to
the formation of a pillared structure. For the SiZr-PCH adsorbent, it is
noticeable a new band about 183.1 eV in the Zr 3d region, which is
assigned to ZrO2 species. In the case Al 2p and Mg 2p regions, these
bands maintain their binding energies, which indicates that montmoril-
lonite framework is not affected. Finally, the bands located in the Ca 2p
region and Na 1s region disappear. This fact indicates a total cationic
exchange, HDTM+ by Na+ and Ca2+ and later removal of the organic
matter in the calcination step.
With regard to the atomic concentration (Table 3), it can be ob-
served how the magnesium, iron and aluminum content decreases
and calcium and sodium disappear of the surface of the adsorbent
when the PCHs are formed, which confirms the modification of the
starting montmorillonite. In addition, it is noticeable a decrease of
iron, magnesium and mainly aluminum content in comparison to the
raw bentonite. This decrease is higher for the SiZr-PCH in comparison
with the Si-PCH, which can be in accordance with partial delamination
of the SiZr-PCH sample by the presence of zirconium giving rise to the
montmorillonite layers more accessible on the surface of the adsorbent.
3.2. Adsorption experiments
Figs. 7 and 8 show the effect of pH in adsorption of RV5R and AB25
on Si-PCH and SiZr-PCH, respectively. In all cases, the maximum amount
adsorbed takes place at lower pH (pH = 2) for AB25 and RV5R dyes.
Previous research has established that the higher adsorption capacity
takes place at pH b 3.0 due to the surface of the clay becomes positively
charged leading to an interaction with the anionic dye (Tabak et al.,
2009). In this case, it can be observed how pHs maintain unaltered
after the adsorption process discarding the interaction of OH+ 2 species
with the anionic species of AB25 and RV5V at lower pH. Thus, the inter-
action between the adsorbent and dyes should be attributed to the in-
teraction by hydrogen bond between the silanol groups of the PCHs
and the electron pairs of the sulfonic groups of the dyes, which are pro-
tonated at low pH as well as amine, hydroxyl and azo groups (Yariv,
1996). The increase of the pH provokes a deprotonation of the \\OH
both the adsorbent and the dyes, as indicates the decreasing the pH
after the adsorption process, leading to the generation of adsorbents
negatively charged which causes a electrostatic repulsion between spe-
cies for adsorbents and dyes.
The kinetic profiles of RV5R and AB25 on Si-PCH and SiZr-PCH are
shown in Figs. 9 and 10, respectively. Both figures display that a fast de-
crease of the dye concentration in the first minutes, reaching the equi-
librium conditions between 40 and 60 min. In addition, both figures
show how the amount adsorbed is slightly higher for SiZr-PCH in com-
parison to Si-PCH for RV5R and AB25 dyes.

(a)
1.0 (a)
1.0

0.8
0.8

0.6
0.6
C/C0

C/C0

0.4
0.4

0.2
0.2

0.0
0 20 40 60 80 100 120 0.0
0 20 40 60 80 100 120
Time (min)
Time (min)
(b) (b)
1.0 1.0

0.8 0.8

0.6 0.6
C/C0

C/C0

0.4 0.4

0.2 0.2

0.0 0.0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)

Fig. 9. Kinetic profile of adsorption for RV5R on Si-PCH at pH = 2 and T = 22 °C: (a) RV5R; Fig. 10. Kinetic profile of adsorption for RV5R on SiZr-PCH at pH = 2 and T = 22 °C: (a)
(b) AB25: (□) 100 ppm (○) 200 ppm and (Δ) 300 ppm. RV5R; (b) AB25: (□) 100 ppm (○) 200 ppm and (Δ) 300 ppm.
42 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44

(a) Table 4
240 Equilibrium adsorption parameters according to Langmuir (L), Langmuir-Freundlich (LF)
and Redlich Peterson (RP) models to dyes adsorption.
200
K a b β KLF qmax (mg g−1) R2 χ2
(mL/mg) (mL/mg)
160
q (mg g )

Acid blue 25 + BG
-1

120 L 14,674.0 301.6 – – – 48.642 0.9825 5.86

LF – – 0.428 – 0.1095 61.022 0.9971 1.13
80 RP 35,306.3 600.4 – 0.907 – 58.798 0.996 1.61

Reactive Violet + BG
40 L 2758.3 109.1 – – – 25.2 0.989 0.823
LF – – 1.870 – 0.0002 23.6 0.991 0.035
0 RP 1829.6 88.2 – 1.116 – 20.7 0.997 0.264
0.00 0.05 0.10 0.15 0.20 0.25 Acid blue 25 + Si-PCH
-1 L 16,371.4 84.7 – – – 193.1 0.995 22.8
Ceq (mg mL )
LF – – 0.806 – 0.0334 209.9 0.998 8.75
RP 20,162.1 91.8 – 0.933 – 219.6 0.997 17.8
(b) Reactive Violet + Si-PCH
240
L 13,125.2 105.3 – – – 124.5 0.993 13.6
LF – – 0.924 – 0.0139 127.0 0.994 14.8
200 RP 12,533.2 103.2 – 1.014 – 121.3 0.994 15.7

160 Acid blue 25 + SiZr-PCH

L 18,553.1 76.6 – – – 242.1 0.992 57.3
q (mg g )
-1

LF – – 0.799 – 0.038 265.9 0.996 35.3

120 RP 22,717.4 82.4 – 0.932 – 275.3 0.994 55.0

80 Reactive Violet + SiZr-PCH

L 15,124.4 88.0 – – – 171.7 0.990 37.1
LF – – 0.807 – 0.031 185.7 0.994 30.0
40 RP 16,707.1 91.2 – 0.967 – 183.0 0.991 41.8

0
0.00 0.05 0.10 0.15 0.20 0.25
modify the electronic density of the adsorbent as well as a slight delam-
-1
Ceq (mg mL ) ination of the porous material, as was shown in XRD, leading to a higher
amount of silanol groups available to the adsorption, especially for the
(c) smaller molecule.
240 In addition, it can be observed how all adsorption isotherms display
a similar pattern. The adsorption takes place mainly at lower Ceq. The
200 non-linearity of the isotherms indicates the presence of chemical inter-
actions between the silanol groups of the porous material and the func-
160
tional groups of the dyes, discarding a physical adsorption by the use of
q (mg g )
-1

adsorbents as molecular sieve.

120
80
40
0 SiZr-PCH, respectively. For RV5R, the maximum adsorption capacity
0.00 0.05 0.10 0.15 0.20 0.25
-1
Ceq (mg mL )
Fig. 11. Adsorption isotherms of RV5R and AB25 on raw bentonite using an initial dye
concentration (25–300 ppm) at pH = 2 and T = 22 °C for (a), Si-PCH (b) and SiZr-PCH
(c): (◄) BG-RV5R; BG-AB25 (►); (■) Si-PCH-RV5R; (●) Si-PCH-AB25; (▲) SiZr-PCH-
RV5R; and (♦) SiZr-PCH-AB25. Theoretical profile: The lines correspond to fitting
(nonlinear regression) of experimental data according to Langmuir model (red line),
Langmuir-Freundlich (green line) and Redlich Peterson (blue line).
The Fig. 11a represents the adsorption isotherm obtained from the
starting material, Si-PCH and SiZr-PCH, respectively. The starting ben-
tonite reaches lower adsorption capacities than those obtained for
both PCHs. With regard to the PCHs, it can observe how RV5R dye
exhibits a lower adsorption capacity for both PCHs possibly by steric ef-
fects due to RV5R dye is bulkier than AB25 dye. Fig. 11b–c also reveal
that SiZr-PCH shows a higher adsorption capacity than Si-PCH. This
fact could be attributed to the presence of zirconium species that can
Langmuir, Langmuir-Freundlich and Redlich Peterson models (Table
4) were used in the modeling of experimental adsorption data. The
equilibrium data were well described using the Langmuir-Freundlich
model for both dyes and both materials, with maximum adsorption ca-
pacity of 209.9 mg g−1 and 265.9 mg g−1 for AB25 in the Si-PCH and
was 127.07 mg g−1 and 185.7 mg g−1 in the case of Si-PCH and SiZr-
PCH, respectively. The raw bentonite displays the lowest adsorption ca-
pacities, due to the low specific surface area and porosity in comparison
to both PCHs. The use of PCHs as adsorbent for the dye adsorption im-
proves the adsorption capacity in comparison to other clay minerals
or other natural sources. Thus, it has been reported q values of
75 mg g− 1 (Karaca et al., 2013) and 39 mg g− 1 (Kuleyin and Aydin,
2011), using modified clays and natural zeolite, respectively, for
Remazol adsorption. In the case of the adsorption of acid blue with
clay minerals, it is reported a q values between 100–150 mg g−1 for
bentonite modified with acid treatment (Juang et al., 1997; Ullah et
al., 2016), 67 mg g−1 for Na-bentonite (Ozcan et al., 2004). These data
indicate that the insertion of pillars improves the dye adsorption capacity.
With regard to the KL constant of the models, which defines the in-
teraction between adsorbate and adsorbent, it is noticeable that the
dye lesser bulky, i.e. AB25, displays higher adsorption values than
RVR5 dye. According to those data shown previously, SiZr-PCH adsor-
bent shows a higher affinity by the adsorbate due to the incorporation
of zirconium species modifies the electronic density and generates
acid sites that must favor the interactions with both dyes.
 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44 43

3.3. Evaluation of materials after the adsorption process Table 5

Elemental analysis (CHNS) of the starting material, Si-PCH and SiZr-PCH before and after
the adsorption process.
In order to confirm the adsorption of the dyes on the raw bentonite
and both PCHs, elemental analysis (CNHS), FTIR and XPS were carried Sample C (wt.%) H (wt.%) N (wt.%) S (wt.%)
out. BG 0.017 0.046 – –
FTIR spectra of the adsorbents after the adsorption process are BG-AB25 0.641 2.268 0.058 0.128
shown in Fig. 12. In all cases, it has not been detected the typical BG-RV5R 0.451 2.073 0.030 0.064
bands of the dyes due to the most intense bands of the dyes overlap Si-PCH 0.021 0.041 – –
with the Si\\O bands. However, in the region of the silanol groups, Si-PCH-AB25 1.031 2.449 0.143 0.287
Si-PCH-RV5R 0.936 2.456 0.114 0.224

SiZr-PCH 0.014 0.042 – –

(a) SiZr-PCH-AB25 1.315 2.917 0.164 0.301
SiZr-PCH-RV5R 1.217 2.718 0.131 0.259
BG
BG-AB25
BG-RV5R
Absorbance (a.u.)

about 3740 cm− 1, it is noticeable how the silanol band disappears

after the adsorption process, confirming that the adsorption process
takes place between the silanol groups of the PCHs and the electron
pair of functional groups of the dyes.
The elemental analysis (CHNS) was carried out to corroborate the
presence of dyes on the adsorbent after the adsorption process (Table
5). CHNS data reveal the existence of nitrogen atoms attributed to the
azo- and amine-groups, and sulfur atoms which are assigned to the
presence of sulfonic groups. The elemental analysis shows how both
Si-PCH and SiZr-PCH have higher amount of nitrogen and sulfur after
4000 3800 3600 3400 3200 3000 the adsorption process than the raw material, confirming those shown
-1 in the adsorption data. In addition, both nitrogen and sulfur content is
Wavenumber (cm ) directly related with adsorbed dye, being higher for AB25 dye, which
is also in accordance with the adsorption data.
(b) The XPS spectra of the PCHs after the adsorption process (Tables 2
and 3) show the arising of new bands located about 401.0 eV, in N 1s re-
gion, attributed to amine groups (Moulder et al., 1992), and another
band in the S 2p region located about 168.4 eV, assigned to the presence
Absorbance (a.u.)

of sulfur in the form of sulfonic groups (Moulder et al., 1992). According

to those shown previously, the atomic concentrations of N and S for Si-
PCH and SiZr-PCH adsorbent are higher than that shown for the starting
3740 material. In addition, the atomic concentrations also show higher con-
centration values of N and S when is adsorbed AB25 due to this com-
pound displays lower volume than RV5R dye.

Si-PCH 4. Conclusion
Si-PCH-AB25
Si-PCH-RV5R
The natural clays are effective precursors to synthesize porous clay
4000 3800 3600 3400 3200 3000 heterostructures for the removal of reactive dyes, concluding that
-1 these adsorbents can remove the remaining dye from aqueous solutions
Wavenumber (cm ) in the treatment of textile wastewater.
The study also concludes that SiZr-PCH adsorbent has a better time
(c) performance in the adsorption of the dyes than Si-PCH adsorbent.
The adsorption process takes place by an interaction between the
silanol groups of the montmorillonite and/or the PCH adsorbent with
functional groups such as amine, hydroxyl or sulfonic groups of the
Absorbance (a.u.)

dyes. This adsorption is influenced by the pH of the system.

The optimum contact time for equilibrium was reached in 40 min for
RV5R and AB25 adsorbents. It can be concluded that dosage increase of
3740 anionic dyes causes a decreases of the efficiency of the adsorption pro-
cess mainly in the case of RV5R dye.
The dye AB25 is better adsorbed in comparison with the dye RV5R
SiZr-PCH due to bulky of each compound.
SiZr-PCH-AB25
SiZr-PCH-RV5R References
Abbassi, R., Yadav, A.K., Kumar, N., Huang, S., Jaffe, P.R., 2013. Modeling and optimization
4000 3800 3600 3400 3200 3000 of dye removal using “green” clay supported iron nano-particles. Ecol. Eng. 61, 366–370.
Al-Khatib, L., Fraige, F., Al-Hwaiti, M., Al-Khashman, O., 2012. Adsorption from aqueous
-1 solution onto natural and acid activated bentonite. Am. J. Environ. Sci. 8, 510–522.
Wavenumber (cm ) Almeida, C.A.P., Debacher, N.A., Downs, A.J., Cottet, L., Mello, C.A.D., 2009. Removal of
methylene blue from colored effluents by adsorption on montmorillonite clay.
Fig. 12. FTIR spectra of the materials after the adsorption process. J. Colloid Interface Sci. 332, 46–53.
44 J.E. Aguiar et al. / Applied Clay Science 135 (2017) 35–44
Anirudhan, T.S., Ramachandran, M., 2015. Adsorptive removal of basic dyes from aqueous
solutions by surfactant modified bentonite clay (organoclay): kinetic and competitive
adsorption isotherm. Process. Saf. Environ. Protect. 95, 215–225.
Barr, T.L., 1990. The nature of the relative bonding chemistry in zeolites: an XPS study. Ze-
olites 10, 760–765.
Briggs, D., Eds, M.P.S., 1992. Practical Surface Analysis. John Wiley & Sons, New York, NY,
USA, p. 1.
Brindley, G.W., 1980. Order–disorder in clay mineral structures. In: Brindley, G.W., Brown,
G. (Eds.), Crystal Structures of Clay Minerals and Their X-ray Identification Mono-
graph No. 5 Mineralogical Society.
Cecilia, J.A., García-Sancho, C., Franco, F., 2013. Montmorillonite based porous clay
heterostructures: Influence of Zr in the structure and acidic properties. Microporous
Mesoporous Mater. 176, 95–102.
Chmel, A., Mazurina, E.K., Shashkin, V.S., 1990. Vibrational spectra and deffect structure of
silica prepared by non-organic sol–gel process. J. Non-Cryst. Solids 122, 285–290.
Farmer, V.C., 1998. Differing effects of particle size and shape in the infrared and Raman
spectra of kaolinite. Clay Miner. 33, 601–604.
Galarneau, A., Barodawalla, A., Pinnavaia, T.J., 1995. Porous clay heterostructures formed
by gallery-templated synthesis. Nature 374, 529–531.
Grundgeiger, E., Hong Lim, Y., Frost, R.L., Ayoko, G.A., Xi, Y., 2015. Application of organo-
beidellites for the adsorption of atrazine. Appl. Clay Sci. 105, 252–258.
İyim, T.B., Güçlü, G., 2009. Removal of basic dyes from aqueous solutions using natural
clay. Desalination 249, 1377–1379.
Juang, R.S., Wu, F.C., Tseng, R.L., 1997. The ability of activated clay for the adsorption of
dyes from aqueous solutions. Environ. Technol. 18, 525–531.
Karaca, S., Gürses, A., Acisli, O., Hassani, A., Kiransan, M., Yikilmaz, K., 2013. Modeling of
adsorption isotherms and kinetics of Remazol red RB adsorption from aqueous solu-
tions by modified clay. Desalin. Water Treat. 51, 2726–2739.
Kıranşan, M., Soltani, R.D.C., Hassani, A., Karaca, S., Khataee, A., 2014. Preparation of
cetyltrimethylammonium bromide modified montmorillonite nanomaterial for ad-
sorption of a textile dye. J. Taiwan Inst. Chem. Eng. 45, 2565–2577.
Kuleyin, A., Aydin, F., 2011. Removal of reactive textile dyes (Remazol brillant blue R and
Remazol yellow) by surfactant-modified natural zeolite. Environ. Prog. Sust. Energy
30, 141–151.
Leodopoulos, C., Doulia, D., Gimouhopoulos, K., 2014. Adsorption of cationic dyes onto
bentonite. Sep. Purif. Rev. 44, 74–107.
Madejová, J., 2003. FTIR techniques in clay mineral studies. Vibrat. Spec. 31, 1–10.
Moulder, J.F., Stickle, W.F., Sobol, P.E., Bomben, K., 1992. Handbook of X-ray Photoelectron
Spectroscopy. Perkin-Elmer Corp, Eden Prairie, MN.
Occelli, M.L., 1998. Surface properties and cracking activity of delaminated clay catalysts.
Catal. Today 2, 339–355.
Ozcan, A.S., Erdem, B., Ozcan, A., 2004. Adsorption of acid blue 193 from aqueous solu-
tions onto Na-bentonite and DTMA-bentonite. J. Colloid Interf. Sci. 280, 44–54.
Ozturk, E., Yetis, U., Dilek, F.B., Demirer, G.N., 2009. A chemical substitution study for a wet
processing textile mill in Turkey. J. Clean. Prod. 17, 239–247.
Pentrák, M., Czímerová, A., Madejová, J., Komadel, P., 2012. Changes in layer charge of clay
minerals upon acid treatment as obtained from their interactions with methylene
blue. Appl. Clay Sci. 55, 100–107.
Pinto, M.L., Saini, V.K., Guil, J.M., Pires, J., 2014. Introduction of aluminum to porous clay
heterostructures to modify the adsorption properties. Appl. Clay Sci. 101, 497–502.
Robens, E., 1999. Adsorption by Powders and Porous Solids. In: Rouquerol, F., Rouquerol,
J., Sing, K. (Eds.), Vak. Forsch. Prax. 11. Academic Press, San Diego, p. 191
Roca Jalil, M.E., Vieira, R.S., Azevedo, D., Baschini, M., Sapag, K., 2013. Improvement in the
adsorption of thiabendazole by using aluminum pillared clays. Appl. Clay Sci. 71,
55–63.
Rouquerol, J., Rouquerol, F., Sing, K.S.W., 2014. Adsorption by Powders & Porous Solids —
Principles, Methodology and Applications (France: 631p).
Schultz, L.G., 1969. Lithium and potassium absorption, dehydroxylation temperature, and
structural water content of aluminous smectites. Clay Clay Miner. 17, 115–149.
Sing, K.S.W., 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.
Tabak, A., Eren, E., Afsin, B., Caglar, B., 2009. Determination of adsorptive properties of a
Turkish sepiolite for removal of reactive blue 15 anionic dye from aqueous solutions.
J. Hazard. Mater. 161, 1087–1094.
Tong, D.S., Zhou, C.H.C., Lu, Y., Yu, H., Zhang, G.F., Yu, W.H., 2010. Adsorption of acid red G
dye on octadecyl trimethylammonium montmorillonite. Appl. Clay Sci. 50, 427–431.
Toor, M., Jin, B., Daí, S., Vimonses, V., 2015. Activating natural bentonite as a cost-effective
adsorbent for removal of Congo-red in wastewater. J. Ind. Eng. Chem. 21, 653–661.
Ullah, Z., Husanin, S., Gul, S., Khan, S., Bangsh, F.K., 2016. Use of HCl-modified bentonite
clay for the adsorption of acid blue 129 from aqueous solutions. Desalin. Water
Treat. 57, 8894–8903.
Vaccari, A., 1999. Clays and catalysis: a promising future. Appl. Clay Sci. 14, 161–198.
Vilarrasa, E.G., Cecilia, J.A., Santos, S.M.L., Cavalcante Jr., C.L., Jiménez, J.J., Azevedo, D.C.S.,
Castellón, E.R., 2014. CO2 adsorption on APTES functionalized mesocellular foams ob-
tained from mesoporous silicas. Microporous Mesoporous Mater. 187, 125–134.
Yagub, M.T., Sen, T.K., Afroze, S., Ang, H.M., 2014. Dye and its removal from aqueous solu-
tion by adsorption: a review. Adv. Colloid Interf. Sci. 209, 172–184.
Yariv, S., 1996. Thermo-IR-spectroscopy analysis of the interactions between organic pol-
lutants and clay minerals. Thermochim. Acta 274, 1–35.
Zent, A.P., Howard, D.J., Quinn, R.C., 2001. H2O adsorption on smectites: application to the
diurnal variation of H2O in the Martian atmosphere. J. Geophys. Res. E: Planets 106,
14667–14674.
Zviagina, B.B., McCarty, D.K., Środon, J., Drits, V.A., 2004. Interpretation of infrared spectra
of dioctahedral smectites in the region of oh-stretching vibrations. Clay Clay Miner.
52, 399–410.