Journal of Molecular Liquids 259 (2018) 384–397

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

A superior adsorbent of CTAB/H2O2 solution−modified organic carbon

rich-clay for hexavalent chromium and methyl orange uptake
from solutions
Mohamed Mobarak a, Ali Q. Selim b, Essam A. Mohamed b, Moaaz K. Seliem b,⁎
a
Physics Department, Faculty of Science, Beni-Suef University, 621, Egypt
b
Geology Department, Faculty of Science, Beni-Suef University, 621, Egypt

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

Article history: Raw clay (RC) rich in organic matter (OM) was separately treated by hydrogen peroxide (H2O2),
Received 22 November 2017 cetyltrimethylammonium bromide (CTAB) and a solution of CTAB/H2O2. The new strategy of RC modification
Received in revised form 27 January 2018 using CTAB/H2O2–solution presented a swollen product (CTAB/H2O2–clay) with porous structure. Raw and mod-
Accepted 2 February 2018
ified clays were characterized by XRD, SEM, FTIR, zeta potential, SBET surface area and tested as adsorbents for
Available online 04 February 2018
hexavalent chromium Cr(VI) and methyl orange (MO) from solutions. Adsorption experiments were conducted
Keywords:
under experimental parameters including pH, shaking time, initial concentrations, adsorbent mass, temperature
Raw clay and ionic strength. CTAB/H2O2−clay gave the highest adsorption capacities for Cr(VI) and MO as compared to the
Organic matter other products at pH 2.0 and 3.0, respectively. Adsorption equilibrium of Cr(VI) and MO was evaluated using
Hexavalent chromium Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models. Langmuir model fitted well the uptake results
Methyl orange and the maximum uptake capacities (qmax) at room temperature (25 °C) were found to be 67.05 and 194.28 mg/g
Adsorption characteristics for Cr(VI) and MO, respectively. The values of mean free energy (E) were N8.0 kJ/mol revealed the chemical na-
Thermodynamic studies ture of Cr(VI) and MO uptake. The pseudo-second-order model with R2 = 0.9999 described well the kinetics
data. Thermodynamic parameters (ΔH0, ΔG0 and ΔS0) indicated that the uptake of Cr(VI) and MO was spontane-
ous and endothermic.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction environment [7,8]. The complex aromatic structure of MO makes it

The pollution of aqueous system due to the discharge of contami-
nated chemicals such as chromium and methyl orange is one of the se-
rious environmental risks. Different industries including paints, steel
fabrication, electroplating, textile and pigments produced large
amounts of chromium as a metal ion into the aquatic environment. In
solutions, chromium can exist in hexavalent Cr(VI) and trivalent Cr
(III) forms with varied toxic characteristics [1,2]. However both of Cr
(III) and Cr(VI) are considered as toxic agents, the toxicity of Cr(VI)
form is great compared to that of the Cr(III) [3,4]. Exposure to Cr(VI)
may cause some hazard diseases including vomiting, stomach ulcers,
liver, kidney and nerve tissue damage as well as cancer in the lungs
[4,5]. The allowed limits of Cr(VI) are 0.05 mg/L and 0.1 mg/L in drinking
water and industrial wastewater, respectively [3,4,6].
Methyl orange, one of the acidic azo dyes, is released into the aquatic
system through printing, textile, paper, plastic and cosmetic industries.
The occurrence of low concentrations of MO in water can inhibit oxygen
and sunlight breakthrough, which frequently harms the aquatic
⁎ Corresponding author.
E-mail address: debakyms@science.bsu.edu.eg (M.K. Seliem).
high stable and more hard to remove from solutions [9]. Furthermore,
the structure MO makes it mutagenic and carcinogenic due to the pres-
ence of aromatic rings [10].
Varied materials have been used as adsorbents for Cr(VI) including
agricultural waste biomass [11], Akadama clay [12], vesicular volcanic
rocks [13], HDTMA-modified montmorillonite, clinoptilolite and glau-
conite [14], Mg-Al hydrotalcite modified kaolinite clay [15], organic
modification of bentonite [16], montmorillonite nanocomposites [3],
treated natural zeolites [17], STAC-activated rectorite [18], raw spent ac-
tivated clay [19], maize bran [20], Fe(II)-treated natural zeolite aggre-
gates [21], cetylpyridinium bentonite [22], riverbed sand [23],
pyrolusite [24], Turkish montmorillonite clay [2], rare earth doped tita-
nium dioxide coated carbon sphere composites [25], carbonaceous
nanofibers [26], molybdenum disulfide coated Mg/Al layered double
hydroxide composites [27] and magnetic porous carbonaceous mate-
rials derived from tea waste [28].
On the other hand, calcined volcanic mud [7], mesoporous carbon
material [8], calcined glycerol-treated nanocrystallined Mg/Al layered
double hydroxides [29], activated carbonaceous material [30], cationic
surfactant coffee waste [31], CTAB-modified wheat straw [10], benton-
ite-supported zero-valent iron [32], porous TiO2 [33], chitosan/MgO

https://doi.org/10.1016/j.molliq.2018.02.014
0167-7322/© 2018 Elsevier B.V. All rights reserved.
 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397
composite [34], CuO/NaA Zeolite [35], multiwalled carbon nanotubes
[36]and coated activated carbon [37] were used for MO adsorption.
The application of clay minerals as adsorbents is attractive because
of their abundant accessibility, non-toxicity, high chemical stability
and low-cost [38]. Clay minerals display no attraction for anionic con-
taminates depending on the fact that their negatively charged surfaces
[39]. Moreover, the structure of clay minerals contains inorganic cations
such as Na+, K+ and Ca2+ makes it ineffective for adsorbing organic
compounds due to the hydrophilic nature [40]. Thus, modification of
clay minerals by different materials such as cationic surfactants is
needed in enhancing their affinity for different anions. The interaction
between clay minerals with negatively charged surfaces and cationic
surfactants includes both cation exchange and hydrophobic bonding
[22]. In addition, hydrogen peroxide (H2O2) was used in chemical acti-
vation (oxidize the organic carbon/matter) or exfoliation of 2:1clay
minerals like vermiculite [41].
To the best of our knowledge, the removal efficiency of organic car-
bon-rich clays modified by H2O2/CTAB solution has not been studied.
Thus, the main objectives of this work were to (a) study the adsorption
capacity of the CTAB/H2O2−clay in uptake of Cr(VI) and MO from aque-
ous solutions as compared to the raw and the different modified clays
(RC, H2O2−clay and CTAB−clay) (b) estimate the removal process as
a function of different factors such as pH, shaking time, initial Cr(VI)
and MO concentrations, adsorbent dose and temperature and (c) inves-
tigate the adsorption characteristics and mechanism controlling Cr(VI)
and MO uptake using different kinetics and isotherms models and (d)
determine thermodynamic parameters related to Cr(VI) and MO ad-
sorption process.
2. Materials and methods
2.1. Materials
The organic carbon rich-clay sample used in the current study was
attained from Fayum area, Egypt. Cetyltrimethylammonium bromide
(Sigma-Aldrich, 99% purity), hydrogen peroxide (30% (w/w) in H2O),
sodium chromate tetrahydrate (Sigma-Aldrich), methyl orange (Fluka,
Switzerland) and distilled water were used in the present study. The re-
quired solution pH was attained using pH meter (Hanna, HI 9025) by
addition of 0.01 M HCl and 0.01 M NaOH solutions.
2.2. Preparation of clay-based adsorbents
2.2.1. Raw clay (RC)
A mass of the dried clay sample (200 g) was subjected to grinding in
a laboratory type ball-mill and sieved to obtain 100 mesh size fractions.
A fixed weight (5 g) of the investigated clay was dispersed in 100 mL de-
ionized water with stirring for 60 min. After centrifuging, the solid
phase was dried at 65 °C for 12 h and homogenized by grinding in a
gate mortar before its application for Cr(VI) and MO adsorption.
2.2.2. H2O2-modified clay (H2O2−clay)
The following procedure was used to treat the studied clay with
H2O2: 5 g of the RC was added to a beaker containing 50 mL of deionized
water. After stirring for 60 min, 50 mL of 30% H2O2 was added to this
mixture. The beaker was covered by watch glasses and heated at 50 °C
with stirring for 60 min. The modification of the RC by H2O2 was re-
peated several times under the same conditions (stirring for 1 h at 50
°C) until the end of effervescence. The solid-liquid parts were separated
by centrifuging and the solid phase was washed by deionized water five
times and then dried in an oven at 65 °C for 12 h.
2.2.3. CTAB-modified clay (CTAB−clay)
The investigated clay was modified by CTAB according to the follow-
ing method: 5 g of the RC was dispersed in 100 mL of distilled water
with stirring for 30 min. A certain mass of CTAB equivalent to 0.007 M
385
was slowly added to the solute ion. Then, the mixture was stirred for
60 min at 50 °C. After separation of the liquid phase, the resulted prod-
uct was washed 7 times with deionized water and dried at 65 °C/12 h.
2.2.4. CTAB/H2O2 solution-modified clay (CTAB/H2O2−clay)
To modify the RC with CTAB/H2O2 solution, CTAB (2.55 g) was added
to 50 mL of 30% H2O2 with stirring until complete dissolving. This solu-
tion was added to a beaker containing a certain amount of the used clay
(5 g) mixed with 25 mL of distilled water. The resulted mixture was
shaken for 60 min at 50 °C. Hydrogen peroxide (30%) is used to oxidize
the organic matter in the investigated RC supporting the connection be-
tween the positive CTAB and the negative RC surface. Then, CTAB is in-
tensely attracted to the negatively charged surface of the clay producing
a swollen product. This attraction can be organized by two processes;
(1) CTAB monolayer formation by the ion exchange and electrostatic in-
teraction and (2) CTAB bilayer creation through hydrophobic interac-
tions [31]. As described above, the final solid product was separated,
washed several times and dried at 65 °C for 12 h.
2.3. Sample characterization
The chemical composition of the RC was determined by the XRF
technique (Philips X-ray fluorescence analyzer model PW/2404). XRD
patterns of the raw and the modified clays were identified using a
Philips APD-3720 diffractometer with Cu Kα radiation (40 kV and
20 mA) at 2°/min of scanning speed. SEM (JSM-6700F, JEOL, Japan)
was used to scan the surface morphology of the investigated samples.
Fourier transform infrared (FTIR analysis) was performed using Bruker
FT/IR-2000 Spectrometer in the range of 400–4000 cm−1 wavenumber.
Zeta potential was measured at 25 °C using Malvern Zetasizer Nano
ZS90. Nitrogen sorption technique was applied to determine the tex-
tural properties of the CTAB/H2O2−clay. N2 adsorption–desorption iso-
therms were measured using Tristar II analyzer. The pore size
distribution was calculated with the Broekhoff-de Boer model and the
pore volume was measured at a P/Po = 0.972. Surface area was calcu-
lated after the samples were degassed at 150 °C under vacuum for 6 h.
Specific surface area (SBET) was calculated according to Brunauer–
Emmett–Teller equation (BET). The Barrett–Joyner–Halenda (BJH)
method was applied to determine the average pore diameter from the
isotherm.
2.4. Effect of pH
To observe the control of pH on Cr(VI) and MO removal, different so-
lutions of Cr(VI) (100 mg/L) and MO (200 mg/L) were kept at varied pH
(2.0, 3.0, 5.0, 7.0, 8.0 and 10.0). Equal masses (0.05 g) of the used solids
(RC, H2O2−clay, CTAB−clay and CTAB/H2O2−clay) were mixed with
25 mL of the adjusted solutions of Cr(VI) and MO. An orbital shaker
(SHO-2D, Germany) was used to shake the mixtures at 200 rpm for
2 h. After centrifuging, the rest of Cr(VI) in solution was determined
Table 1
Chemical composition of the studied RC sample.
Chemical analysis of RC Compounds of RC
SiO2 40.72%
Al2O3 21.23%
TiO2 0.71%
Fe2O3 4.41%
MgO 2.81%
Na2O 1.96%
CaO 1.03%
K2O 0.56%
P2O5 0.21%
Cl 1.79%
SO3 1.81%
H2O + OM 17.87%
CO2 2.86%
386 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397

by ion chromatography (DX-120 ion chromatography). The MO con- [42,43].

centration in solutions was measured using a double beam UV–visible
spectrophotometer (Shimadzu, Model UV 1601, Japan) at λmax = V ðC0–Ct Þ
468 nm. qt ðmg=gÞ ¼ ð1Þ
m

2.5. Adsorption experiments

Standard solutions (1000 mg/L) of Cr(VI) (Sigma-Aldrich) and MO
(Fluka, Switzerland) were prepared by dissolving sodium chromate
(Na2CrO4·4H2O) and MO (C14H14N3NaO3S) in distilled water, respec-
tively. In adsorption experiments, the required concentrations of Cr
(VI) and MO were attained through diluting the prepared stock solu-
tions with deionized water.
2.5.1. Adsorption kinetics
Cr(VI) and MO adsorption kinetics were calculated at room temper-
ature (25 °C) using a mixture of 0.05 g of the CTAB/H2O2−clay and
25 mL of Cr(VI) and MO with concentrations of 100 and 200 mg/L, re-
spectively. At different contact times (5, 30, 60, 120, 240 and
360 min), the mixtures were agitated at 200 rpm for 60 min. After sep-
aration of the solid product, the Cr(VI) and MO concentrations in solu-
tions were determined. The following relations (Eqs. (1) and (2))
were applied to calculate the adsorbed amount (qt) and the percentage
uptake (R %) of Cr(VI) and MO At all the formerly mentioned times
ðC0–CtÞ
Rð%Þ ¼  100 ð2Þ
C0
where C0 (mg/L) is the initial concentration of Cr(VI) and MO, Ct is the
rest concentration of the studied azo-dye and chromate after time (t),
respectively, V is the volume of solution (L) and m is the mass of the
used adsorbent (g). All adsorption experiments including kinetics and
isotherm were carried out three times.
2.5.2. Adsorption isotherms
Equilibrium studies were conducted at room temperature using
25 mL of Cr(VI) and MO with varied initial concentrations (100–
200 mg/L) and (150–400 mg/L), respectively. A certain mass of the
CTAB/H2O2−clay (50 mg) was mixed with the prepared solution
(25 mL) in centrifuge tubes and then, the mixture was shaken at
200 rpm for 60 min using an orbital shaker. After centrifuging, the solu-
tions were analyzed by to determine the final concentrations of Cr(VI)
and MO.

b c

Fig. 1. Characterization of the RC: (a) XRD pattern, (b, c) SEM images and (d) FTIR spectrum.
 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397 387

Fig. 2. Characterization of the CTAB/H2O2−clay: (a, b, c and d) SEM photographs and (e) FTIR spectrum.

2.6. Effect of ionic strength
Ionic strength is considered as one of the important parameters that
control the electrostatic and non-electrostatic interactions between the
investigated contaminates (Cr(VI) and MO) and the CTAB/H2O2−clay
surface. Different solutions with initial NaCl concentrations ranging
from 0 to 10 g/L were used to study the impact of ionic strength on ad-
sorption process. This effect was studied at 25 °C by shaking 0.025 g of
the CTAB/H2O2−clay with 25 mL of Cr(VI) and MO (100 mg/L) for
120 min (200 rpm) at pH 2.0 and 3.0, respectively. The rest

Table 2
Textural analysis of RC and CTAB/H2O2−clay.

Sample Total pore volume (cm3/g) Average pore diameter (Å) Average particle size (Å) BET surface area (m2/g)

RC 0.154 48.42 864.67 69.39

CTAB/H2O2−clay 0.0935 68.04 2835.4 21.16
388 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397
Fig. 3. (a) Nitrogen adsorption-desorption isotherm of CTAB/H2O2−clay, (b) zeta
potential of RC and (c) zeta potential of CTAB/H2O2−clay.
concentrations of Cr(VI) and MO in solutions were determined after
separation of the solid phases by centrifuging.
3. Results and discussions
3.1. Characterization of RC and CTAB/H2O2−clay
Chemical analysis of the investigated RC (Table 1) indicated that the
SiO2/Al2O3 ratio is equal to 1.92 and this value is between the ideal ratios
of kaolinite (1.18) and montmorillonite (2.36) [44]. The low K2O per-
centage (0.56%) may reflect the low content of illite clay mineral in
the RC. The high content of H2O2 + OM (17.87%) reflected the high con-
tent of organic matter in the RC.
The XRD patterns of the investigated RC showed the presence of ka-
olinite and montmorillonite as clay minerals. On the other hand, quartz
with its characteristic diffractions at 3.34 and 4.26 Å was identified as
associated non-clay mineral (Fig. 1a).
SEM images of the RC collected from Fayum area reflected the exis-
tence of particles with flaky particles with irregular shape and size (Fig.
1b). The surfaces of the flaky particles were covered by solid and porous
organic matter displaying variation in size and shape were observed
(Fig.1c).
The FTIR spectrum of RC (Fig.1d) displayed peaks at 3694.27 cm−1
(inner-surface O\\H group), 3625.18 cm−1 (stretching vibrations of
Al\\OH), 3429.95 cm−1 (–OH stretching vibrations) corresponding to
H2O molecules and 1640.63 cm−1 related to the (H\\O\\H) bending
vibrations of adsorbed water onto the clay surface [45,46]. The strong
band at 1029.85 cm−1 was related to the Si\\O stretching vibrations,
while the band at 915.68 cm−1 was attributed to the bending vibrations
of Al\\Al\\OH hydroxyl groups of the clay mineral [47]. The detected
bands at 535.72 and 466.09 cm−1are related to the Si\\O\\Al and
Si\\O\\Si bending vibrations, respectively [46]. Moreover, vibrations
detected at 693.01 and 788.67 cm−1indicated the presence of silicate
minerals as quartz [44].
SEM images of the CTAB/H2O2−clay displayed flaky crystals with
large thickness as compared to the RC (Fig. 2a, b). The interaction be-
tween CTAB/H2O2 solution and the investigated clay led to the forma-
tion of fluffy and swollen product with porous structure compared to
the raw clay (Fig. 2c, d).
The comparison of FTIR spectrum of the CTAB/H2O2−clay (Fig. 2e)
with that of the RC exhibited two new peaks at 2853.66 and
2923.83 cm−1 that are attributed to the symmetric and asymmetric
stretching vibrations of C\\H [3,22]. Also, the noticed peak at
1476.72 cm−1 is related to –CH2 shearing vibration [3]. In addition,
the new band at 3025.84 cm−1 is attributed to the aromatic C\\H
stretching [48]. The occurrence of these different new bands indicated
that the surface alteration of the studied clay was attained after interac-
tion with CTAB/H2O2 solution. Also, the observed peak at 1381.32 cm−1
was related to bending vibration of mechanical-held H2O molecules
[49]. The results of nitrogen adsorption isotherms of RC and CTAB/
H2O2−clay are given in Table 2. The average pore diameter low value
determined using BJH method of RC (48.42 Å) resulted in increasing
its BET surface area (69.39 m2/g) and total pore volume (0.154 cm3/g)
as compared to CTAB/H2O2−clay. The interaction between RC and
CTAB/H2O2−solution led to increasing the pore diameter average of
CTAB/H2O2−clay (68.04 Å) causing a decrease in the SBET to the value
of 21.16 m2/g. The plot of volume adsorbed (cm3/g) versus relative pres-
sure (P/P0) presented the type II of the nitrogen adsorption/desorption
isotherm depending on IUPAC classification (Fig. 3a). The isotherms
have hysteresis loops type H3 reflecting the presence of plate like parti-
cles producing slit-like pores [44]. Based on zeta potential measure-
ments, the RC and CTAB/H2O2−clay surfaces gave values of −24.71
and 5.8 mV, respectively. The shift in RC surface charge may be related
to the interaction between the RC and the CTAB/H2O2 solution (Fig.
3b, c).
3.2. Characterization of the CTAB/H2O2−clay after uptake of Cr(VI) and MO
The SEM photos of Cr(VI) and MO loaded the CTAB/H2O2 −clay
displays the occurrence new shiny Cr(VI) ions in the form dissem-
inated and agglomerated particles over the surface of the adsorbent
(Fig. 4a). The attendance of Cr(VI) ions in the form of shiny parti-
cles was observed in different previous studies [4]. The presence
of granulated separated particles and layers only over the adsor-
bent surface reflected MO adsorption onto the CTAB/H 2 O 2 −clay
(Fig. 4b).
The FTIR spectra of the CTAB/H2O2−clay loaded by Cr(VI) and MO
after adsorption were shown (Fig. 4c, d). After Cr(VI) uptake, the no-
ticed peak at 1381.32 cm−1 was shifted to 1402.07 cm−1indicating
the Cr(VI) bending with hydroxyl groups [4]. The band of the aromatic
C\\H stretching which was observed at 3025.84 cm−1 was changed to
3033.25 cm−1 due to the interaction of Cr(VI) with the CTAB/H2O2−
clay. On the other hand, the bands at 3696.03, 3625.42, 3423.34,
2923.83, 2853.78 cm−1 were slightly shifted after chromate loading
(Fig. 4c). Relating to MO, the peak at 3423.57 cm−1 which characterized
the stretching vibration of –OH groups and interlayered H2O molecules
was shifted to 3437.18 cm−1 showing a broad band [50]. The disappear-
ance of the two bands at 3696.03 and 3025.84 cm−1 reflected the inter-
action between the CTAB/H2O2−clay and MO. The detected bands at
1476.71, 914.44, 789.48, 534.82 and 465.94 cm−1 of the CTAB/H2O2−
clay were slightly changed after MO uptake (Fig. 4d).
 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397 389

Fig. 4. Characterization of the CTAB/H2O2−clay after Cr(VI) and MO uptake: (a, b) SEM images and (c, d) FTIR spectra for Cr(VI) and MO adsorption, respectively.

3.3. Effect of pH
Based on this experiment, the pH value producing the maximum up-
take efficiency of each studied sample for Cr(VI) and MO was deter-
mined. Moreover, adsorption characteristics were evaluated for the
product resulting in the highest adsorption capacity.
The impact of initial pH in the range of 2.0–10.0 on Cr(VI) and MO
adsorption by the RC, H2O2−clay, CTAB−clay and CTAB/H2O2−clay is
shown (Fig. 5a, c). The highest adsorption capacities of Cr(VI) and MO
for all the tested clays (raw and modified) were detected at pH of 2.0
and 3.0, respectively. The Cr(VI) uptake percentages at pH 2.0 gave
values of 32.23, 35.4, 58.35 and 92.91%, but the MO removal percentages
390 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397
Fig. 5. Effect of pH on the uptake of (a, c) Cr(VI) and (b, d) MO by the raw and modified clays.
at pH 3.0 recorded values of 36.25, 40.04, 60.25 and 99.6% for raw clay,
H2O2−clay, CTAB−clay and CTAB/H2O2−clay, respectively. Among all
the above mentioned clays, the CTAB/H2O2−clay exhibited the highest
uptake values for both of Cr(VI) and MO compared to the other clays
(Fig. 5a, c). Thus, the interaction of the CTAB/H2O2−clay with Cr(VI)
Fig. 6. Effect of CTAB/H2O2−clay mass on the uptake of (a) Cr(VI) and (b) MO.
and MO at different values of pH (2.0–10.0) was deeply discussed in
the current study.
Regarding Cr(VI), different oxyanionic types of chromium such as
HCrO− 2− 2−
4 , Cr2O7 and CrO4 can exist in solution based on the pH value
[3,51]. At solution pH in the range from 1.0 and 4.0, the main form of
Cr(VI) is HCrO− 4 [17]. At low pH, the surface of the CTAB/H 2O2−clay
become positively due to the increase of H+ concentration in solu-
tion. Thus, the strong electrostatic attraction between HCrO − 4 and
the positively charged surface of the CTAB/H 2 O 2−clay produced
the great percentages of Cr(VI) uptake with values of 92.91 and
89.25% at pH 2.0 and 3.0, respectively [52]. At solution pH 5.0,
HCrO− 2−
4 was changed to Cr2O7 with high quantity of the later species
[16]. The high content of Cr2O2− 7 which needs two positively active
sites for adsorption process [24] in addition to the deprotonation of
the CTAB/H2O 2 −clay led to a decrease in the uptake percentage
(50.38%) of Cr(VI) at pH 5.0. By increasing pH N6.0, CrO2−
4 is the dom-
inant type and this form exhibits a repulsive force with the partially
deprotonated surface groups of the CTAB/H2O2−clay [17,18]. Under
alkaline conditions, the concentration of OH− ions increases in solu-
tions and the hydroxide ions have higher attraction to the CTAB/
H2O2−clay surface than CrO2− 4 [51,53]. Due to the shifting of chro-
mate species and the presence of competitive hydroxide ions under
basic conditions (pH N 7.0), the CTAB/H2 O2 −clay gave the lowest
values of Cr(VI) uptake (13.43) and (11.72%) at pH 8.0 and 10.0,
respectively.
Concerning MO (Fig. 5b, d), the protonation of the MO monova-
lent anions by the high H+ concentration clarified the low removal
percentage of MO (28.26%) at pH 2.0 [54]. Electrostatic repulsion be-
tween the protonated MO and positively charged sites of the CTAB/
H2 O2 –clay surface decreased the uptake process. At pH 3.0, the
highest removal efficiency recorded by the CTAB/H 2O 2 −clay
(99.6%) could be related to the degree of MO ionization (pKa =
3.46) [33]. The strong electrostatic attraction between the positive
charge sites of CTAB/H2O2−clay and anionic MO resulted in a nota-
ble increase in MO uptake. The formation of hydrogen bonding –
SO3H at pH 3.0 is an added factor causing the higher MO uptake. At
pH N 7.0 (basic conditions), the competition between the non-pro-
tonated MO and OH− in solution remarkably decreased the removal
of MO by the CTAB/H2O2−clay surface giving values of 16.56% and
16.38% at pHs 8.0 and 10.0, respectively [31,55]. According to the
 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397 391

Fig. 7. Kinetic studies of Cr(VI) uptake by the CTAB/H2O2−clay, (a) effect of contact time, (b) pseudo-first-order (c) pseudo-second-order and (d) intra-particle diffusion models.

above pH results, the effects other experimental parameters were
carried out at pHs 2.0 and 3.0 for Cr(VI) and MO, respectively.
3.4. Effect of CTAB/H2O2−clay mass
Different masses of the CTAB/H2O2−clay (50–300 mg) were mixed
with 25 mL of Cr(VI) and MO with initial concentrations of 150 and
400 mg/L, respectively. The sorption percentages of Cr(VI) and MO
from solutions at the selected masses are shown in Fig. 6. Concerning
Cr(VI), the removal efficiency gave values of 33.49% and 96.45%, with in-
creasing the CTAB/H2O2−clay dose from 0.05 to 0.2 g (Fig. 6a). Using
the same doses of the CTAB/H2O2−clay (0.05–2.0), the uptake effi-
ciency of MO increased from 68.89% to 98.02% (Fig. 6b). The rise the
CTAB/H2O2−clay surface area resulted in increasing the removal effi-
ciency of Cr(VI) and MO due to the presence of added sorption sites
[56,57]. Above 200 mg of the CTAB/H2O2−clay, the uptake percentages

Fig. 8. Kinetic studies of MO uptake by the CTAB/H2O2−clay, (a) effect of contact time, (b) pseudo-first-order (c) pseudo-second-order and (d) intra-particle diffusion models.
392 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397

Table 3
Adsorption kinetics models of Cr(VI) and MO uptake by the CTAB/H2O2−clay.

Kinetic model Linear form Parameters Refs.

Pseudo-first-order ln(qe − qt) = ln qe − k1t qt (mg/g): removed amount of Cr(VI) and MO at time t. [63]
qe (mg/g): equilibrium adsorption uptake
k1(g/mg min): rate constant of the first-order adsorption.
Pseudo- second-order t
¼k 1
þ qt k2(g/mg min): rate constant of the second-order adsorption [64]
2 −qe
qt 2
e
1/2
Intra-particle diffusion qt = kp t +C kp (mg/g min0.5): intraparticle diffusion rate constant . [69]
C (mg/g): intercept of the line.

of Cr(VI) and MO increased slightly (Fig.6a, b). Further increase in the
adsorbent mass over 0.2 g had no effect in Cr(VI) and MO uptake indi-
cating the stage with the maximum adsorption limit at the used concen-
trations [58,59].
3.5. Effect of shaking time
The influence of contact time (5–360 min) on Cr(VI) and MO adsorp-
tion by the studied modified clay (CTAB/H2O2−clay) is shown (Figs 7a,
8a). From the start of shaking time to 5 min (stage 1), it was noticed that
the adsorbed amounts qt of Cr(VI) and MO gave values of 24.76 and
89.62 mg/g, respectively. The percentage of Cr(VI) and MO uptake by
the CTAB/H2O2−clay was very rapid in this step due to the accessibility
of a great number of binding sites for adsorption [43,60]. By increasing
the contact time to 60 min (stage 2), the pervious adsorbed values of
Cr(VI) and MO increased gradually to 30.42 and 95.98 mg/g, respec-
tively. After 60 min to the end of shaking time (stage 3), the values of
qt were nearly constant due to the saturation of active sites and the at-
tainment of dynamic equilibrium stage [42,61,62]. Accordingly, the up-
take of Cr(VI) and MO was rapid and 60 min is considered as sufficient
shaking time to achieve equilibrium.
3.6. Adsorption kinetics
To test the experimental data of Cr(VI) and MO uptake by the CTAB/
H2O2−clay, the pseudo-first-order [63] and the pseudo-second-order
[64] equations (Table 3) were applied in the current study. The
pseudo-first-order parameters were determined by plotting ln (qe −
qt) versus time (t) (Figs. 7b, 8b) and the results are shown in Table 4.
From the plot of t/qt against t (Figs. 7c, 8c), the parameters of pseudo-
second-order equation were calculated and the obtained results are
shown in Table 4. Based on the attained kinetics parameters and the cor-
relation coefficient values (R2), the pseudo-second-order model de-
scribed well the Cr(VI) and MO adsorption process. This is due to the
high values of R2 (0.9999) for Cr(VI) and MO as compared to the
pseudo-first-order equation with R2 = 0.906 and 0.438 for Cr(VI) and
MO, respectively. In addition, the matching between the values of qe
(theoretical) and qe (experimental) of the pseudo-second-order equa-
tion exhibited a good applicability of this model for Cr(VI) and MO ad-
sorption and indicated that chemisorption process could be a rate
contolling-step [65–68].
throughout Cr(VI) and MO removal by the CTAB/H2O2−clay indicated
that the adsorption process including both boundary layer and
intraparticle diffusion [49,74,75]. The values of the intercept (C =
26.104 for Cr(VI) and 91.236 mg/g for MO) (Table 4) confirmed the
large thickness of the boundary layer diffusion, especially during MO
adsorption. The removal efficiency of the CTAB/H2O2−clay was found
to be high for MO as compared to Cr(VI). This could be attributed to
the type of interaction between the CTAB/H2O2−clay and the studied
contaminates (Cr(VI) and MO). The interaction in Cr(VI) case was elec-
trostatic between the positively charged surface of the adsorbent and
the negatively charged chromate species found at pH 2.0. This electro-
static interaction type was found through MO adsorption between the
negative groups (SO3−) and the positive active sites (R−N+ (CH3)2)
of the CTAB/H2O2−clay at pH 3.0 [31]. Moreover, hydrophobic−hydro-
phobic interaction type between hydrophobic parts of the CTAB/H2O2−
clay and MO could be involved during the adsorption process. The con-
tribution of the two interaction kinds in MO adsorption led to increasing
the uptake efficiency of the CTAB/H2O2−clay for MO.
3.8. Adsorption isotherms
Adsorption equilibrium shows the interaction of Cr(VI) and MO mol-
ecules with the adsorbent (CTAB/H2O2–clay) at equilibrium state. In the
present study, Langmuir, Freundlich, Temkin and Dubinin–
Radushkevich (D–R) (Table 5) were used to analyze the attained exper-
imental adsorption data for Cr(VI) and MO.
3.8.1. Langmuir isotherm
According to the hypothesis of Langmuir isotherm [76], the Cr(VI)
and MO adsorption takes place at homogenous active sites onto the
CTAB/H2O2−clay. The plot of Ce/qe against Ce (Figs. 9a, 10a.) was used
to calculate the parameters of Langmuir model (b and qmax) and the re-
sults are listed in Table 6. The equilibrium parameter (Rs) or separation
factor [77] of the Langmuir isotherm classifies the nature of adsorption
process to be either (unfavourable: Rs N 1, linear: Rs = 1, favourable: 0 b
Rs b 1 and irreversible: Rs = 0) was determined from the following
equation [78,79]:
1
Rs ¼ ð3Þ
1 þ kL C 0

3.7. Adsorption mechanism

Table 4
Parameters of the applied kinetics models for Cr(VI) and MO uptake by the CTAB/H2O2
To study the uptake mechanism of Cr(VI) and MO by the CTAB/H2O2 −clay.
−clay, the intra-particle diffusion [69] model was used (Table 3). The
relation between the removed amount (qt) and the root square of shak- Kinetic model Parameters R2

ing time (t 0.5) of the intra-particle diffusion model (Figs. 7d, 8d) Pseudo-first-order qe (cal)(mg/g ) −1
k1(min )
showed multi-linear steps reflecting the difference in Cr(VI) and MO ad- Cr(VI) 3.243 0.02 0.906
MO 3.77 0.0034 0.438
sorption rate during the first and the last periods [70,71]. The first sharp
Pseudo-second-order qe (cal)(mg/g ) k2(min−1)
stage (t b 5 min) could be governed by the influence of boundary layer Cr(VI) 31.27 0.017 0.99997
diffusion or exterior mass transfer [72,73]. The second step (5 b t MO 96.158 0.025 0.99999
b 60 min) of the model reflected the control of pore-diffusion stage Intra-particle diffusion kp(mg/g min0.5) C(mg/g)
[59]. The last gentle step (60 b t b 360 min) displayed the stage at Cr(VI) 0.327 26.104 0.664
MO 0.321 91.236 0.593
which equilibrium was achieved. The occurrence of different steps
 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397 393

Table 5
Adsorption isotherms models for Cr(VI) and MO uptake by the CTAB/H2O2−clay.

Isotherm model Linear form Parameters Refs.

Langmuir Ce
¼q 1
þ Ce Ce (mg/L): equilibrium concentration of the resting MO in the solution [76]
qe max b qmax
qe (mg/g): removed amount of Cr(VI) and MO at equilibrium.
qmax (mg/g): maximum adsorption capacity
b (L/mg): Langmuir constant
Freundlich logqe ¼ logK F þ n1 logC e KF (mg/g): Cr(VI) and MO adsorption capacity. [80]
n: heterogeneity factor.
Temkin qe = B ln A + B ln Ce A (L/mg): the equilibrium binding constant [82]
B (mg/g): the amount of adsorption heat.
Dubinin–Radushkevich lnqe = ln qm − βε2 β(mol2/kJ2): D-R constant [83]
ε (kJ2/mol2): Polanyil potential,
equal to RT ln ð1 þ C1e Þ.
R: universal gas constant (8.31 J/mol K).
T (K): absolute temperature.
qm (mg/g): theoretical adsorption capacity.

The calculated Rs values were found to be 0.05–0.096 and 0.0012–
0.0031 for Cr(VI) and MO, respectively. Therefore, the equilibrium pa-
rameters were in the range of 0–1 indicating a favourable adsorption
condition.
3.8.2. Freundlich isotherm
Freundlich isotherm [80] is based on multilayer adsorption on active
sites with varied heat of adsorption (heterogeneous surfaces) [7]. From
the plot of log qe against log Ce (Figs. 9b, 10b), KF and n values were de-
termined and the results are given in Table 6. The n values were found to
be 4.50 and 4.74 for Cr(VI) and MO, respectively indicating good adsorp-
tion characteristics (2 bn b 10) [38]. In addition, the value of 1/n were
less than one (Table 6) representing a chemisorption process [81].
3.8.3. Temkin isotherm
According to this isotherm model [82], the adsorption heat of all
molecules in the layer would decrease linearly instead of logarithmi-
cally with coverage [35]. The plot of qe versus ln Ce (Figs. 9c, 10c) was
applied to determine the parameters of Temkin isotherm model (A
and B) and the results are shown in Table 6.
3.8.4. Dubinin–Radushkevich isotherm
The D–R isotherm model indicates that the uptake nature of Cr(VI)
and MO is either chemical or physical adsorption [60]. The parameters
of the D–R model were obtained (Figs. 9d, 10d) and listed in Table 6.
The mean energy of was calculated as follows [83]:
1
E ¼ pffiffiffiffiffiffi ð4Þ
2β
The determined E values were 9.404 and 13.849 kJ/mol for Cr(VI)
and MO, respectively. These values limited from 8 to 16 kJ/mol indicated
that the Cr(VI) and MO adsorption by the CTAB/H2O2−clay is chemical
[84].
Based on the correlation coefficient (R2) of the four applied models
(Table 6), Langmuir isotherm for Cr(VI) (R2 = 0.991 ) and MO (R2 =
0.998 ) well fitted the experimental data. Thus, the uptake of Cr(VI)

Fig. 9. Linear isotherm studies of Cr(VI) uptake by the CTAB/H2O2−clay, (a) Langmuir, (b) Freundlich (c) Temkin and (d) D-R models.
394 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397

Fig. 10. Linear isotherm studies of MO uptake by the CTAB/H2O2−clay, (a) Langmuir, (b) Freundlich (c) Temkin and (d) D-R models.

and MO occurred onto homogenous active sites of the investigated
CTAB/H2O2−clay.
3.9. Comparison of the CTAB/H2O2−clay with other studies
The maximum adsorption capacities of Cr(VI) and MO by the CTAB/
H2O2−clay of the present study in comparison with different materials
testified by former studies is shown in Table 7. According to the deter-
mined qmax of Cr(VI) (67.05 mg/g) and MO (194.28 mg/g), the modified
clay (CTAB/H2O2−clay) is considered as an active adsorbent material
for Cr(VI) and MO.
endothermic nature of Cr(VI) and MO uptake by the CTAB/H2O2−clay
[85]. Enhancement the adsorption capacity of the CTAB/H2O2−clay
may be attributed to either the decrease in the boundary layer thickness
surroundings the sorbent or increase in the active sites of the adsorbent
surface [86,87].
Thermodynamic parameters such as Gibbs free energy (ΔG0), ad-
sorption heat (ΔH0) and entropy (ΔS0) were determined using the fol-
lowing equations [88].
ΔG0 ¼ −R T ln K L ð5Þ

3.10. Effect of temperature and thermodynamic studies

Table 7
The influence of temperature ranging from 303 to 328 K on the re- Maximum adsorption capacity for Cr(VI) and MO by different materials in comparison
moved amounts of Cr(VI) and MO was investigated using a mass of with the CTAB/H2O2−clay of the current study.
CTAB/H2O2−clay (0.025 g) mixed with fixed initial concentration Type Adsorbent Adsorption capacity Reference
(100 mg/L) of Cr(VI) and MO. At the lowest temperature (303K) the qmax (mg/g)
adsorbed amounts of Cr(VI) and MO recorded values of 17.43 and Cr(VI) Agricultural waste biomass 0.3–0.8 [11]
77.16 mg/g, respectably. By rising temperature to 328 K, the removed Carbon slurry 15.2 [5]
amounts of Cr(VI) and MO increased to 29.62 and 88.50 mg/g, respec- Natural Akadama clay 4.3 [12]
tively. The increase in adsorption with temperature revealed the Raw and modified green alga 31–35 [74]
Activated clay 24.1 [92]
Modified natural zeolites 3.5–8.8 [17]
Table 6 Modified rectorite 21 [18]
Parameters of isotherms models for Cr(VI) and MO uptake by the CTAB/H2O2−clay. Carbonaceous adsorbents 53.8–56.5 [85]
Treated rice husks 8.5–10.4 [84]
Isotherm Model Parameters R2
CTAB/H2O2−clay 67.05 The current
Langmuir qmax(mg/g) KL (L/mg) study
Cr(VI) 67.052 0.095 0.991 MO Bottom ash 3.62 [93]
MO 194.278 2.152 0.988 De-Oiled Soya 16.66 [93]
Freundlich KF(mg/g) 1/n Activated clay 16.78 [94]
Cr(VI) 22.933 0.222 0.831 Treated coal powder 18.52 [95]
MO 121.609 0.211 0.815 Orange peel 20.5 [96]
Temkin A(L/mg) B(mg/g) Banana peel 21 [97]
Cr(VI) 2.859 11.097 0.859 Na-montmorillonite 24 [32]
MO 109.609 27.234 0.871 Nano-composite films 29.41 [97]
Dubinin–Radushkevich qm (mg/g ) E(kJ/mol) Activated wheat straw 50.4 [10]
Cr(VI) 75.856 9.404 0.844 CTAB/H2O2−clay 194.28 The current
MO 268.656 13.849 0.814 study
 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397 395

positive due to the increase of the randomness through the interaction

between solid and solution during Cr(VI) and MO uptake [91].

3.11. Effect of ionic strength

The influence of ionic strength on Cr (VI) and MO adsorption onto

the CTAB/H2O2−clay is shown in Fig. 12. With increasing NaCl concen-
tration from 0 to 10 g/L, the adsorbed amounts were found to be in the
range of 16.89–10.82 mg/g and 72.45–69.02 mg/g for Cr (VI) and MO,
respectively. This decrease in the removed amounts could be attributed
to the competition between Cr (VI) and MO anions with Cl− for the
sorption active sites. The influence of ionic strength on Cr (VI) uptake
is high as compared to that of MO (Fig. 12) indicating that the main
mechanism of Cr (VI) uptake was related to electrostatic attraction
[31]. On the other hand, the slight influence of ionic strength in MO ad-
sorption reflected the presence of hydrophobic interaction between hy-
drophobic parts of the CTAB/H2O2−clay and MO. The little influence of
ionic strength on MO adsorption onto the CTAB/H2O2−clay agrees with
previous studies [29,31].

4. Conclusion

The current study highlighted the viability of treated organic carbon-

Fig. 11. Plot of lnKL and 1/T for calculation of thermodynamic parameters for (a) Cr(VI) and
(b) MO uptake by the CTAB/H2O2−clay.
ΔG0 ¼ ΔH0 −T ΔS0 ð6Þ
ΔS0 ΔH0
ln K L ¼ − ð7Þ
R RT
where, R is the universal gas constant (8.314 J/mol K).
Langmuir isotherm model, the best fitted model, was used to deter-
mine the values of ΔG0 in Eq. (5) [89]. The values of ΔH0 and ΔS0 were
calculated via plot of ln KL against 1/T (Fig. 11a, b). From this plot, the
values of ΔH0 and ΔS0 values were calculated and the attained results
were listed in Table 8. For Cr(VI) and MO, the ΔH0 was positive with
values of 31.23 and 48.60 kJ/mol, respectively. This indicates that the re-
moval of Cr(VI) and MO increases with temperature (endothermic na-
ture) [85]. The negative ΔG0 values (Table 8) designates the
spontaneous nature of Cr(VI) and MO onto the CTAB/H2O2−clay and
feasibility of the adsorption process [60]. Moreover, the ΔG0 values be-
came further negative with rising temperature as shown (Table 8)
reflecting the improvement of Cr(VI) and MO uptake [1]. The obtained
ΔG0 values for Cr(VI) and MO were greater than −10 kJ/mol, reflecting
the chemical mechanism of the adsorption process [90]. The ΔS0 were
rich clay by H2O2, CTAB and a solution of CTAB/H2O2 for Cr(VI) and MO
uptake from solutions. The CTAB/H2O2−clay (porous and swollen)
product exhibited the highest adsorption capacities for Cr(VI) and MO
compared to the other modified clays at pHs 2.0 and 3.0, respectively.
Kinetic data displayed that equilibrium for Cr(VI) and MO adsorption
was attained after 60 min of shaking time. The adsorption results of Cr
(VI) and MO showed well agreement with Langmuir and pseudo-sec-
ond-order equations. The maximum adsorption capacity (qmax) of the
CTAB/H2O2−clay for MO (194.28 mg/g) was found to be better than
Cr(VI) (67.05 mg/g) due to the involvement of electrostatic and hydro-
phobic interactions in MO adsorption. The uptake of Cr(VI) and MO was
governed by boundary layer followed by intraparticle diffusion. The cal-
culated mean free energy (E) values were 9.404 kJ/mol for Cr(VI) and
13.849 kJ/mol for MO indicating chemical adsorption. Thermodynamic
parameters reflected the endothermic and spontaneous nature of Cr
(VI) and MO adsorption by the CTAB/H2O2−clay. Based on the attained
results, the CTAB/H2O2−clay could be applied as a promising sorbent
for Cr(VI) and MO uptake from solutions. Further studies are needed
to evaluate the effects of CTAB and H2O2 concentrations and the interval
time between CTAB−H2O2 interaction on the structure and efficiency of
the solid product.

Table 8
Thermodynamics parameters for Cr(VI) and MO uptake by the CTAB/H2O2−clay.

Thermodynamics ΔH(0) ΔS(0) ΔG(0) (kJ/mol)

(kJ/mol) (kJ/mol)
303 K 313 K 323 K 328 K

Cr(VI) 31.23 0.104 −0.224 −1.208 −2.062 −2.94

Fig. 12. Effect of ionic strength on the adsorbed amount of Cr(VI) and MO by the CTAB/
MO 48.604 0.182 −6.639 −8.347 −9.797 −11.445
H2O2−clay.
396 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397
Acknowledgements
This work was financed by the Support and Project Finance Office,
Beni-Suef University (200-4579/2017). Authors are gratitude to Mr.
Nashaat Ahmed, the XRD technician in the Faculty of postgraduate,
Beni-Suef University for his cooperation during the conduction of the
laboratory work.
References
[1] M.S. Gasser, G.A. Morad, H.F. Aly, Batch kinetics and thermodynamics of chromium
ions removal from waste solutions using synthetic adsorbents, J. Hazard. Mater. 142
(2007) 118–129.
[2] S.T. Akar, Y. Yetimoglu, T. Gedikbey, Removal of chromium (VI) ions from aqueous
solutions by using Turkish montmorillonite clay: effect of activation and modifica-
tion, Desalination 244 (2009) 97–108.
[3] G. Wang, Y. Hua, X. Su, S. Komarneni, S. Ma, Y. Wang, Cr(VI) adsorption by montmo-
rillonite nanocomposites, Appl. Clay Sci. 124–125 (2016) 111–118.
[4] M. Bansal, D. Singh, V.K. Garg, A comparative study for the removal of hexavalent
chromium from aqueous solution by agriculture wastes' carbons, J. Hazard. Mater.
171 (2009) 83–92.
[5] V.K. Gupta, A. Rastogi, A. Nayak, Adsorption studies on the removal of hexavalent
chromium from aqueous solution using a low cost fertilizer industry waste material,
J. Colloid Interface Sci. 342 (2010) 135–141.
[6] C. Wang, Z. Xu, G. Ding, X. Wang, M. Zhao, S.S.H. Ho, Y. Li, Comprehensive study on
the removal of chromate from aqueous solution by synthesized kaolin supported
nanoscale zero-valent iron, Desalin. Water Treat. 57 (11) (2015) 1–14.
[7] A.A. Jalil, S. Triwahyono, S.H. Adam, N.D. Rahim, M.A.A. Aziz, N.H.H. Hairom, N.A.M.
Razali, M.A.Z. Abidin, M.K.A. Mohamadiah, Adsorption of methyl orange from aque-
ous solution onto calcined Lapindo volcanic mud, J. Hazard. Mater. 181 (2010)
755–762.
[8] N. Mohammadi, H. Khani, V.K. Gupta, E. Amereh, S. Agarwal, Adsorption process of
methyl orange dye onto mesoporous carbon material–kinetic and thermodynamic
studies, J. Colloid Interface Sci. 362 (2011) 457–462.
[9] E.R. Garcia, R.L. Medina, M.M. Lozano, I.H. Perez, M.J. Valero, A.M.M. Franco, Adsorp-
tion of azo-dye Orange II from aqueous solutions using a metal-organic framework
material: iron- benzenetricarboxylate, Materials 7 (2014) 8037–8057.
[10] Y. Su, Y. Jiao, C. Dou, R. Han, Biosorption of methyl orange from aqueous solutions
using cationic surfactant-modified wheat straw in batch mode, Desalin. Water
Treat. 52 (2014) 6145–6155.
[11] U.K. Garg, M.P. Kaur, V.K. Garg, D. Sud, Removal of hexavalent chromium from aque-
ous solution by agricultural waste biomass, J. Hazard. Mater. 140 (2007) 60–68.
[12] Y. Zhao, S. Yang, D. Ding, J. Chen, Y. Yang, Z. Lei, C. Feng, Z. Zhang, Effective adsorp-
tion of Cr (VI) from aqueous solution using natural Akadama clay, J. Colloid Interface
Sci. 395 (2013) 198–204.
[13] E. Alemayehu, S. Thiele-Bruhn, B. Lennartz, Adsorption behaviour of Cr(VI) onto
macro and micro-vesicular volcanic rocks from water, Sep. Purif. Technol. 78
(2011) 55–61.
[14] T. Bajda, Z. Kłapyta, Adsorption of chromate from aqueous solutions by HDTMA-
modified clinoptilolite, glauconite and montmorillonite, Appl. Clay Sci. 86 (2013)
169–173.
[15] D. Lin, S. Zhou, L. Lu, C. Shi, Y. Ling, Y. Xiu, L. Li, Adsorption of hexavalent chromium
onto kaolin clay based adsorbent, J. Cent. South Univ. 21 (2014) 3918–3926.
[16] B. Sarkar, Y. Xi, M. Megharaj, G.S.R. Krishnamurti, D. Rajarathnam, R. Naidu, Remedi-
ation of hexavalent chromium through adsorption by bentonite based Arquad®
2HT-75 organoclays, J. Hazard. Mater. 183 (2010) 87–97.
[17] Y. Zeng, H. Woo, G. Lee, J. Park, Removal of chromate from water using surfactant
modified Pohang clinoptilolite and Haruna chabazite, Desalination 257 (2010)
102–109.
[18] H. Hong, W.T. Jiang, X. Zhang, L. Tie, Z. Li, Adsorption of Cr(VI) on STAC-modified
rectorite, Appl. Clay Sci. 42 (2008) 292–299.
[19] C.H. Weng, Y.C. Sharma, S. Chu, Adsorption of Cr(VI) from aqueous solutions by
spent activated clay, J. Hazard. Mater. 155 (2008) 65–75.
[20] S.H. Hasan, K.K. Singh, O. Prakash, M. Talat, Y.S. Ho, Removal of Cr(VI) from aqueous
solutions using agricultural waste ‘maize bran’, J. Hazard. Mater. 152 (2008)
356–365.
[21] G. Lv, Z. Li, W.T. Jiang, C. Ackley, N. Fenske, N. Demarco, Removal of Cr(VI) from
water using Fe(II)-modified natural zeolite, Chem. Eng. Res. Des. 92 (2014)
384–390.
[22] A.A. Atia, Adsorption of chromate and molybdate by cetylpyridinium bentonite,
Appl. Clay Sci. 41 (2008) 73–84.
[23] Y.C. Sharma, C.H. Weng, Removal of chromium(VI) from water and wastewater by
using riverbed sand: kinetic and equilibrium studies, J. Hazard. Mater. 142 (2007)
449–454.
[24] M. Gheju, I. Balcu, G. Mosoarca, Removal of Cr(VI) from aqueous solutions by ad-
sorption on MnO2, J. Hazard. Mater. 310 (2016) 270–277.
[25] J. Wang, Y. Liang, O. Jin, J. Hou, B. Liu, X. Li, W. Chen, T. Hayat, A. Alsaedi, X. Wang,
Simultaneous removal of graphene oxide and chromium(VI) on the rare earth
doped titanium dioxide coated carbon sphere composites, ACS Sustain. Chem. Eng.
5 (2017) 5550–5561.
[26] W. Cheng, C. Ding, X. Wang, Z. Wu, Y. Sun, S. Yu, T. Hayat, X. Wang, Competitive
sorption of As(V) and Cr(VI) on carbonaceous nanofibers, Chem. Eng. J. 293
(2016) 311–318.
[27] J. Wang, P. Wang, H. Wang, J. Dong, W. Chen, X. Wang, S. Wang, T. Hayat, A. Alsaedi,
X. Wang, Preparation of molybdenum disulfide coated Mg/Al layered double hy-
droxide composites for efficient removal of chromium(VI), ACS Sustain. Chem.
Eng. 5 (2017) 7165–7174.
[28] T. Wen, J. Wang, S. Yu, Z. Chen, T. Hayat, X. Wang, Magnetic porous carbonaceous
material produced from tea waste for efficient removal of As(V), Cr(VI), humic
acid, and dyes, ACS Sustain. Chem. Eng. 5 (2017) 4371–4380.
[29] W. Yao, S. Yu, J. Wang, Y. Zou, S. Lu, Y. Ai, N.S. Alharbi, A. Alsaedi, T. Hayat, X. Wang,
Enhanced removal of methyl orange on calcined glycerol-modified nanocrystallined
Mg/Al layered double hydroxides, Chem. Eng. J. 307 (2017) 476–486.
[30] T.A. Saleh, A.A. Al-Saadi, V.K. Gupta, Carbonaceous adsorbent prepared from waste
tires: experimental and computational evaluations of organic dye methyl orange,
J. Mol. Liq. 191 (2014) 85–91.
[31] R. Lafi, A. Hafiane, Removal of methyl orange (MO) from aqueous solution using cat-
ionic surfactants modified coffee waste (MCWs), J. Taiwan Inst. Chem. Eng. 58
(2016) 424–433.
[32] Z.X. Chen, X.Y. Jin, Z. Chen, M. Megharaj, R. Naidu, Removal of methyl orange from
aqueous solution using bentonite-supported nanoscale zero-valent iron, J. Colloid
Interface Sci. 363 (2011) 601–607.
[33] S. Asuha, X.G. Zhou, S. Zhao, Adsorption of methyl orange and Cr(VI) on mesoporous
TiO2 prepared by hydrothermal method, J. Hazard. Mater. 181 (2010) 204–210.
[34] Y. Haldorai, J.J. Shim, An efficient removal of methyl orange dye from aqueous solu-
tion by adsorption onto chitosan/MgO composite: a novel reusable adsorbent, Appl.
Surf. Sci. 292 (2014) 447–453.
[35] E. Mekatel, S. Amokrane, A. Aid, D. Nibou, M. Trari, Adsorption of methyl orange on
nanoparticles of a synthetic zeolite NaA/CuO, C. R. Chim. 18 (2015) 336–344.
[36] Y. Yao, B. He, F. Xu, X. Chen, Equilibrium and kinetic studies of methyl orange ad-
sorption on multiwalled carbon nanotubes, Chem. Eng. J. 170 (2011) 82–89.
[37] J. Pal, M.K. Deb, D.K. Deshmukh, D. Verma, Removal of methyl orange by activated
carbon modified by silver nanoparticles, Appl Water Sci 3 (2013) 367–374.
[38] V. Vimonses, S. Lei, B. Jina, C.W.K. Chow, C. Saint, Kinetic study and equilibrium iso-
therm analysis of Congo Red adsorption by clay materials, Chem. Eng. J. 148 (2009)
354–364.
[39] B.S. Krishna, D.S.R. Murty, B.S.J. Prakash, Surfactant-modified clay as adsorbent for
chromate, Appl. Clay Sci. 20 (2001) 65–71.
[40] M.K. Seliem, S. Komarneni, R. Parette, H. Katsuki, F.S. Cannon, M.G. Shahien, A.A.
Khalil, I.M. Abd El-Gaid, Perchlorate uptake by organosilicas, organo-clay minerals
and composites of rice husk with MCM-48, Appl. Clay Sci. 53 (2011) 621–626.
[41] C. Marcos, I. Rodriguez, Exfoliation of vermiculites with chemical treatment using
hydrogen peroxide and thermal treatment using microwaves, Appl. Clay Sci. 87
(2014) 219–227.
[42] M.K. Seliem, S. Komarneni, T. Byrne, F.S. Cannon, M.G. Shahien, A.A. Khalil, I.M. Abd
El-Gaid, Removal of perchlorate by synthetic organosilicas and organoclay: kinetics
and isotherm studies, Appl. Clay Sci. 71 (2013) 21–26.
[43] A.M. Zayed, A.Q. Selim, E.A. Mohamed, M.S.M. Abdel Wahed, M.K. Seliem, M.
Sillanpaa, Adsorption characteristics of Na-A zeolites synthesized from Egyptian ka-
olinite for manganese in aqueous solutions: response surface modeling and optimi-
zation, Appl. Clay Sci. 140 (2017) 17–24.
[44] A. Sdiri, T. Higashi, T. Higashia, F. Jamoussi, N. Tase, Evaluating the adsorptive capac-
ity of montmorillonitic and calcareous clays on the removal of several heavy metals
in aqueous systems, Chem. Eng. J. 172 (2011) 37–46.
[45] M. Alkan, C. Hopa, Z. Yilmaz, H. Guler, The effect of alkali concentration and solid/liq-
uid ratio on the hydrothermal synthesis of zeolite NaA from natural kaolinite, Micro-
porous Mesoporous Mater. 86 (2005) 176–184.
[46] F. Kooli, L. Yan, Chemical and thermal properties of organoclays derived from highly
stable bentonite in sulfuric acid, Appl. Clay Sci. 83–84 (2013) 349–356.
[47] A. Dutta, N. Singh, Surfactant-modified bentonite clays: preparation, characteriza-
tion, and atrazine removal, Environ. Sci. Pollut. Res. 22 (2015) 3876–3885.
[48] A. Akelah, A. Rehab, M. Abdelwahab, M.A. Betiha, Synthesis and thermal properties
of nanocomposites based on exfoliated organoclay polystyrene and poly
(methylmethacrylate), Nano 3 (2017) 20–29.
[49] D. Gusain, V. Srivastava, M. Sillanpää, Y.C. Sharma, Kinetics and isotherm study on
adsorption of chromium on nano crystalline iron oxide/hydroxide: linear and non-
linear analysis of isotherm and kinetic parameters, Res. Chem. Intermed. 42 (2016)
7133–7151.
[50] P. Zhang, T. Wang, G. Qian, D. Wu, R.L. Frost, Removal of methyl orange from aque-
ous solutions through adsorption by calcium aluminate hydrates, J. Colloid Interface
Sci. 426 (2014) 44–47.
[51] A.Q. Selim, E.A. Mohamed, M. Mobarak, A.M. Zayed, M.K. Seliem, S. Komarneni,
Cr(VI) uptake by a composite of processed diatomite with MCM-41: isotherm,
kinetic and thermodynamic studies, Microporous Mesoporous Mater. 260
(2018) 84–92.
[52] N. Ballav, A. Maity, S.B. Mishra, High efficient removal of chromium(VI) using gly-
cine doped polypyrrole adsorbent from aqueous solution, Chem. Eng. J. 198–199
(2012) 536–546.
[53] Y. Wu, X. Ma, M. Feng, M. Liu, Behavior of chromium and arsenic on activated car-
bon, J. Hazard. Mater. 159 (2008) 380–384.
[54] B. Tanhaei, A. Ayati, F.F. Bamoharram, M. Lahtinen, M. Sillanpää, A novel magnetic
Preyssler acid grafted chitosan nano adsorbent: synthesis, characterization and ad-
sorption activity, J. Chem. Technol. Biotechnol. 91 (2015) 1452–1460.
[55] M.V. Subbaiah, D.S. Kim, Adsorption of methyl orange from aqueous solution by
aminated pumpkin seed powder: kinetics, isotherms, and thermodynamic studies,
Ecotoxicol. Environ. Saf. 128 (2016) 109–117.
[56] S.H. Asl, M. Ahmadi, M. Ghiasvand, A. Tardast, R. Katal, Artificial neural network
(ANN) approach for modeling of Cr(VI) adsorption from aqueous solution by zeolite
prepared from raw fly ash (ZFA), J. Ind. Eng. Chem. 19 (2013) 1044–1055.
 M. Mobarak et al. / Journal of Molecular Liquids 259 (2018) 384–397
[57] M. Omraei, H. Esfandian, R. Katal, M. Ghorbani, Study of the removal of Zn(II) from
aqueous solution using polypyrrole nanocomposite, Desalination 271 (2011)
248–256.
[58] M. Kapur, M.K. Mondal, Competitive sorption of Cu(II) and Ni(II) ions from aqueous
solutions: kinetics, thermodynamics and desorption studies, J. Taiwan Inst. Chem.
Eng. 45 (2014) 1803–1813.
[59] M.K. Seliem, S. Komarneni, Equilibrium and kinetic studies for adsorption of iron
from aqueous solution by synthetic Na-A zeolites: statistical modeling and optimi-
zation, Microporous Mesoporous Mater. 228 (2016) 266–274.
[60] S. Chowdhury, R. Mishra, P. Saha, P. Kushwaha, Adsorption thermodynamics, kinet-
ics and isosteric heat of adsorption of malachite green onto chemically modified rice
husk, Desalination 265 (2011) 159–168.
[61] S.S. Ibrahim, H.S. Ibrahim, N.S. Ammar, H.H. Abdel Ghafar, T.S. Jamil, M. Farahata, Ap-
plicability of Egyptian diatomite for uptake of heavy metals, Desalin. Water Treat. 51
(2013) 2343–2350.
[62] S. Ma, J. Zhang, D.X. Liu, Surface complexation modeling calculation of Pb(II) adsorp-
tion onto the calcined diatomite, Appl. Surf. Sci. 359 (2015) 48–54.
[63] S. Langergren, B.K. Svenska, Veternskapsakad, Zur theorie der sogenannten adsorp-
tion geloester stoffe, Handlingar, 24, 1898 1–39.
[64] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (5) (1999) 451–465.
[65] K.S. Hui, C.Y.H. Chao, S.C. Kot, Removal of mixed heavy metal ions in wastewater by
zeolite 4A and residual products from recycled coal fly ash, J. Hazard. Mater. B127
(2005) 89–101.
[66] B.H. Hameed, A.L. Ahmad, K.N.A. Latiff, Adsorption of basic dye (methylene blue)
onto activated carbon prepared from rattan sawdust, Dyes Pigments 75 (2007)
143–149.
[67] Z. Ma, Q. Li, Q. Yue, B. Gao, X. Xu, Q. Zhong, Synthesis and characterization of a novel
super-absorbent based on wheat straw, Bioresour. Technol. 102 (2011) 2853–2858.
[68] Y. Lu, B. Jiang, L. Fang, F. Ling, J. Gao, F. Wu, X. Zhang, High performance NiFe layered
double hydroxide for methyl orange dye and Cr(VI) adsorption, Chemosphere 152
(2016) 415–422.
[69] J.C. Weber, W.J. Morris, Proceedings of International Conference on Water Pollution
Symposium, Pergamon, 2, 1962 231–266.
[70] I.A.W. Tan, B.H. Hameed, A.L. Ahmad, Equilibrium and kinetic studies on basic dye
adsorption by oil palm fibre activated carbon, Chem. Eng. J. 127 (2007) 111–119.
[71] M.K. Seliem, E.A. Mohamed, A.Q. Selim, M.G. Shahien, M.R. Abukhadra, Synthesis of
Na-A zeolites from natural and thermally activated Egyptian kaolinite: characteriza-
tion and competitive adsorption of copper ions from aqueous solutions, Int. J. Bioas-
says 4 (2015) 4423–4430.
[72] T.K. Naiya, A.K. Bhattacharya, S. Mandal, S.K. Das, The sorption of lead(II) ions on rice
husk ash, J. Hazard. Mater. 163 (2009) 1254–1264.
[73] A. Sdiri, T. Higashi, F. Jamoussi, S. Bouaziz, Effects of impurities on the removal of
heavy metals by natural limestones in aqueous systems, J. Environ. Manag. 93
(2012) 245–253.
[74] V.K. Gupta, A.K. Shrivastava, N. Jain, Biosorption of chromium from aqueous solu-
tions by green algae Spirogyra species, Water Res. 35 (2001) 4079–4085.
[75] B.H. Hameed, M.I. El-Khaiary, Malachite green adsorption by rattan sawdust: iso-
therm, kinetic and mechanism modeling, J. Hazard. Mater. 159 (2008) 574–579.
[76] I. Langmuir, The constitution and fundamental properties of solids and liquids, J. Am.
Chem. Soc. 38 (1916) 2221–2295.
[77] K.R. Hall, L.C. Eagleton, A. Acrivos, T. Vermeulen, Pore solid diffusion kinetics in fixed
bed adsorption under constant pattern conditions, Ind. Eng. Chem. Fundam. 5
(1966) 212–223.
397
[78] L.L. Lian, L.P. Guo, C.J. Guo, Adsorption of Congo red from aqueous solutions onto Ca-
bentonite, J. Hazard. Mater. 161 (1) (2009) 126–131.
[79] S.V. Ramanaiah, S.V. Mohan, P.N. Sarma, Adsorptive removal of fluoride from aque-
ous phase using waste fungus (Pleurotus ostreatus 1804) biosorbent: Kinetics eval-
uation, Ecol. Eng. 31 (2007) 47–56.
[80] H.M.F. Freundlich, Over the adsorption in solution, J. Phys. Chem. 57 (1906)
385–471.
[81] K.Y. Foo, B.H. Hameed, Insights into the modeling of adsorption isotherm systems,
Chem. Eng. J. 156 (2010) 2–10.
[82] M.J. Temkin, V. Pyzhev, Recent modifications to Langmuir Isotherms, Acta
Physicochim. URSS 12 (1940) 217–222.
[83] M.M. Dubinin, L.V. Radushkevich, The equation of the characteristic curve of the ac-
tivated charcoal, Proc. Acad. Sci. USSR, Phys. Chem. Sect. 55 (1947) 331–337.
[84] W.S.W. Ngah, S. Fatinathan, Adsorption characterization of Pb(II) and Cu(II) ions
onto chitosan-tripolyphosphate beads: kinetic, equilibrium and thermodynamic
studies, J. Environ. Manag. 91 (2010) 958–969.
[85] M. Jain, V.K. Garg, K. Kadirvelu, Adsorption of hexavalent chromium from aqueous
medium onto carbonaceous adsorbents prepared from waste biomass, J. Environ.
Manag. 91 (2010) 949–957.
[86] A.K. Meena, G.K. Mishra, P.K. Rai, C. Rajagopal, P.N. Nagar, Removal of heavy metal
ions from aqueous solutions using carbon aerogel as an adsorbent, J. Hazard.
Mater. 122 (2005) 161–170.
[87] G. Kiani, M. Dostali, A. Rostami, A. Khataee, Adsorption studies on the removal of
Malachite Green from aqueous solutions onto halloysite nanotubes, Appl. Clay Sci.
54 (2011) 34–39.
[88] M. Auta, B.H. Hameed, Modified mesoporous clay adsorbent for adsorption isotherm
and kinetics of methylene blue, Chem. Eng. J. 17 (2012) 502–509.
[89] E.C. Lima, M.A. Adebayo, F.M. Machado, in: C.P. Bergmann, F.M. Machado (Eds.),
Chapter 3- Kinetic and Equilibrium Models of Adsorption in Carbon Nanomaterials
as Adsorbents for Environmental and Biological Applications, Springer 2015,
pp. 33–69 ISBN 978–3–319-18,874-4.
[90] X. Liu, L. Zhang, Removal of phosphate anions using the modified chitosan beads:
adsorption kinetic, isotherm and mechanism studies, Powder Technol. 277 (2015)
112–119.
[91] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Adsorption of basic dye on high-surface-area
activated carbon prepared from coconut husk: equilibrium, kinetic and thermody-
namic studies, J. Hazard. Mater. 154 (2008) 337–346.
[92] W. Li, Y. Tang, Y. Zeng, Z. Tong, D. Liang, W. Cui, Adsorption behavior of Cr(VI) ions
on tannin-immobilized activated clay, Chem. Eng. J. 193–194 (2012) 88–95.
[93] A. Mittal, A. Malviya, D. Kaur, J. Mittal, L. Kurup, Studies on the adsorption kinetics
and isotherms for the removal and recovery of Methyl Orange from wastewaters
using waste materials, J. Hazard. Mater. 148 (2007) 229–240.
[94] Q. Ma, F. Shen, X. Lu, W. Bao, H. Ma, Studies on the adsorption behavior of methyl
orange from dye wastewater onto activated clay, Desalin. Water Treat. 51 (2013)
3700–3709.
[95] Z. Liu, A. Zhou, G. Wang, X. Zhao, Adsorption behavior of methyl orange onto mod-
ified ultrafine coal powder, Chin. J. Chem. Eng. 17 (2009) 942–948.
[96] G. Annadurai, R.S. Juang, D.J. Lee, Use of cellulose-based wastes for adsorption of
dyes from aqueous solutions, J. Hazard. Mater. 92 (2002) 263–274.
[97] R. Jiang, Y.Q. Fu, H.Y. Zhu, J. Yao, L. Xiao, Removal of methyl orange from aqueous so-
lutions by magnetic maghemite/chitosan nanocomposite films: adsorption kinetics
and equilibrium, J. Appl. Polym. Sci. 125 (2012) 540–549.