Surfaces and Interfaces 14 (2019) 117–126

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Surfaces and Interfaces

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

Removal of congo red dye from aqueous solutions using znfe2o4/sio2/ T

Tragacanth gum magnetic nanocomposite as a novel adsorbent
Tahereh Etemadiniaa, Behnam Barikbina, Ali Allahresanib,
⁎

a
Social Determinants of Health Research Center, Environmental Health Engineering Department, Health School Birjand University of Medical Sciences, Birjand, Iran
b
Department of Chemistry, Faculty of Science, University of Birjand, Birjand, Iran

ARTICLE INFO ABSTRACT

Keywords: In the present study, the zinc ferrite nanoparticle was synthesized, and the silica layer was fixed on this na-
Nanocomposite, ZnFe2O4 noparticle. Then, the nanocomposite surface of the natural biocompatible polymer of tragacanth gum (TG) was
SiO2 modified and nanocomposite was identified by transmission electron microscope (TEM), X-ray diffraction (XRD),
Tragacanth gum thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and vibrational sample
Congo red
magnetometer (VSM). The synthesized nanocomposite was used for congo red (CR) removal from aqueous so-
Removal
lutions. The effect of different parameters such as pH, contact time, initial dye concentrations, adsorbent dosage
and solvent temperature for adsorption process has been studied. The results showed that in the optimum
conditions pH = 5, contact time = 60 min, initial dye concentration = 60 mg/L, and adsorbent dose = 0.2 g/L,
was maximum adsorption capacity was 159.90 mg/g. Furthermore, according to the results, it was determined
that the adsorption of CR follows the Langmuir isotherm and the second-order kinetics. The thermodynamic
parameters showed that the adsorption process of Znfe2o4/SiO2/Tragacanth gum nanocomposite was a spon-
taneous and endothermic process.

1. Introduction
Water pollution by the dye is one of the major threats to human
health and the environment [1]. There are currently about 10,000
different types of synthetic dyes, and more than 10 × 105 tons of them
are produced annually throughout the world, with a high percentage of
them being azo dyes. Dye wastewater is produced from various sources
such as paper, leather, plastics, food, cosmetics, textiles, pharmaceu-
ticals, etc. [2–4]. Discharge of dyed sewage into the receiving waters, in
addition to creating unpleasant scenes and popular protests, prevents
sunlight penetration into deep layers of water, which causes disorder in
photosynthesis performance of aquatic plants, occurrence of eu-
trophication phenomena, increasing sewage hardness, turbidity, death
and destruction of creatures in surface waters [3]. Also, some dyes due
to their aromatic molecular structure may be carcinogenic, mutagenic,
and teratogenic [5]. Congo red (CR), an anionic dye called Iupac (1-
Naphthalene sulfonic acid, 3, 3 - (4,4-baina phenylene bis-azo), bis (4-
amino) di-Sodium) has a benzidine agent (Fig. 1) [6]. The sewage from
the printing, textile, plastic and paper industries contains high con-
centrations of a toxic dye of CR. CR is a toxic dye that causes serious
eyes, skin, alimentary tract, genital, and respiratory irritation and is
carcinogen and mutagenic. In many countries, its use is prohibited, but
it is widely used in several countries yet [1,6–8]. So, the removal of this
dyes is necessary. To remove dyed pollutants, use different methods like
surface adsorption, coagulation, flocculation, advanced oxidation pro-
cesses, ozonation, zonal filter, and biological purification [6]. Due to
the different advantages such as less cost, easy designation, high flex-
ibility in designation, high ability in removal of small molecular matters
(like dye and organic materials), little sensibility against fluctuations,
easy performance, and resistance to toxic substances, surface adsorp-
tion is an effective method in removing of dyes [3]. In the recent years,
nanoparticle and especially magnetic nanoparticles usage as adsorbents
for removing of various pollutants have increased because of some
significant features such as easy separation by an external magnetic
field, easy synthesis of nanoparticles, fast performing of adsorption
process, and high surface ratio to volume [9]. Magnetic nanoparticles
are sensible to oxidation and aggregation because of having a very high
specific surface and existing of Van der Waals forces and oxidize very
fast, so modifying of the surface of the magnetic nanoparticles using
organic materials or minerals is required [10]. Silica cover protects
from magnetic core and prevents from the oxidation of iron. Also, silica
cover can provide a good platform for modifying on the surface of the
nanoparticle by creating Si-OH groups [11]. In recent years, several
biological polymers were studied to cover and modify the surface of the

⁎
Corresponding author.
E-mail address: a_allahresani@birjand.ac.ir (A. Allahresani).

https://doi.org/10.1016/j.surfin.2018.10.010
Received 30 March 2018; Received in revised form 30 October 2018; Accepted 31 October 2018
Available online 02 November 2018
2468-0230/ © 2018 Elsevier B.V. All rights reserved.
T. Etemadinia et al.
Fig. 1. molecular structure of CR.
nanoparticles [12–15]. Tragacanth gum (TG) is one of the most abun-
dant heterogeneous anion polysaccharides and biological polymers
with a high molecular weight (840 Kilo Dalton) [16,17]. Existing of
agent groups of primary and secondary hydroxyls, and carboxylic acid
and epoxy group in the structure of TG provide good positions for re-
acting with reactive groups like functional groups [18]. ZnFe2O4/SiO2/
Tragacanth gum nanocomposite is a biocompatible and non-toxic ad-
sorbent that does not produce harmful side-effects. In the present study,
firstly, magnetic nano-particle of Zinc-ferrite (ZnFe2O4) was synthe-
sized, then its surface was modified by Silica and then TG (biocompa-
tible polymer), and the application of synthesis nanocomposite was
investigated in the removal of CR dye. To optimize of the removal
process, some parameters including solution pH, contact time, pollutant
concentration, adsorbent dosage, temperature, and thermodynamics of
the process were tested. Additionally, four models of isotherms (Lang-
muir, Freundlich, Temkin, and Dubinin Radushkevich) and two models
of adsorption kinetics (Pseudo-first-order and Pseudo-second-order)
were analyzed. Also, for identifying nanoparticles, different techniques
such as TEM, XRD, TGA, FT-IR, and VSM were used.
2. Material and methods
2.1. Material and instrument
In the present study, in order to synthesis of ZnFe2O4/SiO2/TG
nanocomposite and performing of adsorption tests iron nitrate (Fe
(NO3)3, 9H2O), zinc nitrate (Zn (NO3)2, 6H2O), sodium hydroxide
(NaOH), ethylenediamine, tetra-ethyl orthosilicate (TEOS), potassium
persulfate, methyl meta acrylate, ascorbic acid, and CR dye manu-
factured by Merck company were used. Also, for identifying of the nan
adsorbent and measuring of samples the X-ray diffraction device (XRD)
model X’ Pert Pro, analytical company, vibration test sample magnet-
ometer (VSM) model 7400, transmission electron microscopy (TEM)
model Zeiss-EM10C-100 KV Germany, Fourier transform infrared
spectroscopy (FT-IR) model AVATAR370 made in the USA, thermo-
gravimetric analysis (TGA) model STA1500 from Rheometric scientific
company, UV–vis spectrophotometer model (UV–Vis spectro-
photometer T80 + , PG Instrument Ltd), and pH-meter (pH meter
Knick, 765 Climatic) were used.
2.2. Preparation of the adsorbent
2.2.1. Synthesis of ZnFe2O4 nanoparticle
13.4 g of Iron (III) nitrate (Fe (NO3)3) and 4.9 g Zinc nitrate (Zn
(NO3)2) in 50 mL distilled water were dissolved (first solution). In the
other balloon, 4.2 g NaOH was dissolved in 70 mL distilled water and
3 mL ethylene diamine (ED) (second solution). Then, the first solution
was added slowly and drop by drop into the second solution. The so-
lution was heated about 45–60 min at a temperature of 90 °C. Then, the
solution was washed several times by water and ethanol. Synthesized
Zinc-ferrite nanoparticle was put in the vacuum Oven, for 7 h and in
80 °C.
The powder was calcined for 1 h at 600 °C with increasing rate of
10 °C/min [19].
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Surfaces and Interfaces 14 (2019) 117–126
2.2.2. Synthesis of ZnFe2O4/SiO2
0.5 g synthesized ZnFe2O4 nanoparticle from the previous step
weighed and were added into it 20 mL distilled water, 60 mL ethanol,
and 1 mL ammonia 25%. The mixture obtained was dispersed for
30 min in an ultrasonic bath. 0.5 mL of tetraethyl orthosilicate (TEOS)
was mixed with 10 mL ethanol and was added to the solution of con-
taining nanoparticles. The resulted solution was mixed up for 24 h at
room temperature. At last, the solution was washed several times by
water and ethanol and nanoparticles were separated by magnet and
they were dried in a vacuum oven at 80 °C and for 7 h [20].
2.2.3. Synthesis of ZnFe2O4/SiO2/TG nanocomposite
Firstly, 1 g TG was dissolved in 250 mL distilled water at 70 °C in a
glass balloon then, 2 g of ZnFe2O4/SiO2 nanoparticles was added to the
solution under stirring at 1200 rpm. Then, 6 mL of methyl methacrylate
and 1.35 g of ascorbic acid were added, and the solution was mixed up
for 30 min. Then, 1.35 g of K2S2O8 was added to the solution, and the
solution was mixed up for another 1 h at room temperature. Finally, the
sample was washed by acetone several times and modified nano-
composite was separated by a magnet. The sample was dried under
vacuum at 60 °C for six hours [16].
2.3. Adsorption studies
All of the adsorption tests were done in laboratory scale and a batch
system on the synthetic samples. The influence of different parameters
such as initial pH of the solution (5–11), contact time (5–120 min),
adsorbent dosage (0.2 to 2 g/L), and temperature (15–45 °C) was tested
in the application of removal and capacity of adsorption of ZnFe2O4/
SiO2/TG nanocomposite. Then, nanocomposite was separated by an
external magnetic field, and the remained concentration of the dye was
measured by spectrophotometer UV–Vis at 497 nm.
In all stages of the test, efficiency and capacity of adsorption were
calculated by Eqs. (1) and (2):
C 0 Ct
% Removal = × 100
C0 (1)
C0 Ct
qe = ×V
m (2)
where C0 is the initial concentration in mg/L, Ct is the concentration
in t time in mg/L, qe is the capacity of dye adsorption in mg/g, m is the
dosage of adsorbent in g, and V is the volume of the sample in lit [16].
In order to identify pH of isoelectric point or point of zero charges
(PZC) pHzpc, 50 mL deionized water was added to balloon, then pH of
deionized water in the range of 2 to 12 was set by HCl and NaOH 0.1 N.
Afterwards, 0.025 g of ZnFe2O4/SiO2/TG nanocomposite was added to
each one of erlenns and were put on the shaker with 200 rpm for 24 h,
after passing 24 h the final pH of the solution was measured by pH-
meter. The initial pH chart was drawn versus the final pH, and the
crossing point of two curves was introduced as the pH of isoelectric
point.
2.4. Thermodynamic parameters
The test with keeping constant of optimal parameters, (pH, contact
time, adsorbent dosage, and dye concentration) was done at tempera-
tures of 15, 25, 35, and 45 °C. Then the thermodynamic constants of
surface adsorption including the changes of Gibbs free energy (∆G°),
changes of entropy (∆S°), and changes of enthalpy (∆H°) were in-
vestigated. In this stage, we used the Eqs. (3)–(5) to extract thermo-
dynamic constants.
Cs
K=
Cs (3)
G= RT lnK (4)
T. Etemadinia et al. Surfaces and Interfaces 14 (2019) 117–126

lnK =
S H
R RT
where K is the thermodynamic equilibrium constant, Cs is the absorbed
dye concentration in the solution by the adsorbent (mg/L), Ce is the
concentration of remained dye in the solution in equilibrium manner
(mg/L), R is the global gas constant (R = 8.3144 J.mol−1.K−1), and T is
the absolute temperature in Kelvin [21].
q e=B lnAT + BlnCe (11)
(5)
where Qe is the amount of absorbed matter in the adsorbent in the
equilibrium time (mg/g), Ce is the equilibrium concentration of the
absorbed matter (mg/L), B is the constant of Temkin (KJ/mol), and AT
is the connection constant of Temkin equation (L/g).
2.6. Adsorption kinetics

2.5. Adsorption isotherms models
2.5.1. Langmuir isotherm model
Theory of Langmuir isotherm model describes the cover of mono-
layer absorbed matter in a homogeneous absorbent level [22]. The
linear equation of the Langmuir is defined as Eq. (6):
Ce 1 Ce
= +
qe KL qm qm (6)
where Ce is the equilibrium concentration of absorbed matter (mg/L),
qe is the amount of absorbed matter in equilibrium time (mg/g), Kl is
the Langmuir constant (l/mg), and Qm is the maximum amount of ad-
sorption of single-layer (mg/L).
The main feature of Langmuir equation is separation factor (RL) that
is defined as the Eq. (7):
1 ZnFe2O4/SiO2 and ZnFe2O4/SiO2/TG nanocomposite. The FT-IR spec-
RL =
1 + bC0 (7)
where b is Langmuir constant (L/mg), RL indicates of isotherm shape, to
favorable adsorption 0˂ RL ˂ 1, for unfavorable adsorption RL˃ 1, for
linear adsorption RL = 1, and for irreversible adsorption RL = 0 [22].
2.5.2. Freundlich isotherm model
This model, in opposition to Langmuir's model, is based on het-
erogeneous surface that have unequal energies. Its empirical equation is
defined as Eq. (8):
logQe = log Kf + 1/ n log Ce (8)
where Ce is equilibrium concentration of the absorbed matter (mg/L),
qe is the amount of absorbed matter in the equilibrium time (mg/g), n is
the indicator of the desirability extent of the adsorption process, and Kf
is the amount of capacity of adsorbent adsorption in (mg/g(l/mg)1/n).
The parameters of 1/n and n, in Freundlich equation can determine
desirability of the adsorption process. If 1/n is less than 1, it shows
desirability of adsorption process by Freundlich's isotherm model [22].
2.5.3. Dubinin Radushkevich isotherm model
In order to the estimation of porosity and free energy of adsorption,
Dubinin Radushkevich model is used [22]. In this model, it is assumed
that the curves of adsorption porosity are related to adsorbent porosity.
The linear equation of this model is as follow (9) [23].
Models of pseudo-first and second order kinetics were used to cal-
culate the resulted data from the experiment to predict kinetic para-
meters of CR adsorption. The equations of pseudo-first and second order
kinetics are defined as Eqs. (12) and (13) [26].
K1t
log(q e qt) = logq e
2/303 (12)
t 1 t
= +
qt K2 qe2 qe (13)
3. Results and discussion
3.1. Characterization adsorbent
Fig 2 shows the FT-IR spectra of the ZnFe2O4 nanoparticle,
trum of ZnFe2O4 NPS shows (Fig 2-a), tensile vibrations in 562 and
453 cm-1 are related of Zn-O and Fe-O, respectively. Also, the observed
vibrations in 3405 cm-1 are related to the tensile vibrations of OeH
[11,27]. Furthermore, vibrational picks in frequencies of 1087 and
959 cm-1 are respectively related to tensile links Si-O-Si and Si-OH
[28,29] and show consolidation of silica on nanoparticles (Fig 2-b). In
the spectra of FT-IR related to ZnFe2O4/SiO2/TG nanocomposite (Fig 2-
c), in addition to mentioned vibrational picks, other important vibra-
tional picks in 3329, 2945, 1746 and 1638 cm-1 are respectively related
to the tensile links OeH-, CeH, C = O, C = C. Existing of absorbent
picks in frequencies of 1228 and 1138 cm-1 is related to the tensile link
of CeO [30]. Existing of vibrating bands (2945, 1746, 1638, 1228, and
1138 cm-1) is approval to the consolidation of TG cover on ZnFe2O4/
SiO2 nanocomposite.
Fig. 3 shows the XRD spectra of ZnFe2O4 nanoparticle, ZnFe2O4/
SiO2 and ZnFe2O4/SiO2/TG nanocomposite. In the Fig (3-a) 2Ɵ (degree)
is observed equally to 30.03, 35.35, 42.95, 49.53, 56.74, and 62.33 that
is related to the presence of plates 220, 311, 400, 422, 511, and 440.
XRD of ZnFe2O4 NPS implies on the formation of spinel cube structure
with spatial groups of Fd-3 m. Intensity maximum is observed in 35.36°.
The size of ZnFe2O4 NPS was calculated 12 nm by achieving from
characteristics of the basic pick (311) and Debye Scherrer Eq. (14) [31]
D=
k.
B cos Ø (14)

Ln(q e) = Ln(qm) 2
(9) where D is the size of the crystal drop, λ is the frequency of the X-ray,

where Qe is the amount of absorbed matter in the equilibrium time

(mg/g), qm is the maximum amount of adsorption (mg/g), β (constant
of the equation) porosity factor, and ε polanyi potential that is defined
as Eq. (10).

1
=RT 1n 1 +
Ce (10)
−1 −1
where R is the global constant of gas (R = 8.3144 J.mol .K ) and T
is the temperature (Kelvin).

2.5.4. Temkin isotherm model

The Temkin isotherm model shows between adsorbate/adsorbate
interactions [24,25]. The linear form of Temkin isotherm is as Eq. (11),
[22]. Fig. 2. FT-IR spectra of (a): ZnFe2O4 (b): ZnFe2O4/SiO2 (c): ZnFe2O4/SiO2/TG.

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T. Etemadinia et al.
Fig. 3. XRD pattern of (a): ZnFe2O4 (b): ZnFe2O4/SiO2 (c): ZnFe2O4/SiO2/TG.
and B is the width of its maximum pick in half of the altitude.
Investigation of XRD spectra of ZnFe2O4/SiO2 nanocomposite
(Fig. 3-b) showed that the synthesized nanocomposite has a crystalline
structure. In addition, 2Ɵ (degree) equaling with 30.03, 35.35, 42.95,
49.53, 56.74, and 62.33 is related to the plates 220, 311, 400, 422, 511,
and 440. The presence of a created pick in 2Ɵ = 23–27˚ is related to
amorphous silica and is approval of stabilizing of the silica layer [11].
Also, the size of nanoparticles using Scherrer equation according to the
features of the greatest width of the pick in the plate 311 and intensity
of angle was calculated 35.35 and nearly 15 nm. Investigation of XRD
pattern of ZnFe2O4/SiO2/TG nanocomposite (Fig. 3-c) showed that
synthesized nanocomposite also has a crystal structure. In addition to
2Ɵ observed in previous patterns, appeared 2Ɵ in angle of 30.88°
proves the presence of amorphous TG on the nanoparticle [32]. Also,
the size of above nanocomposite using Scherrer equation and features
of the width of the main pick (311) was calculated nearly 24 nm.
Fig. 4 shows the TEM of ZnFe2O4 nanoparticle, ZnFe2O4/SiO2 and
ZnFe2O4/SiO2/TG nanocomposite. The results showed that the size of
ZnFe2O4 NPS and ZnFe2O4/SiO2, ZnFe2O4/SiO2/TG nanocomposite are
13, 17 and 25 nm respectively that is similar to the results of XRD and
images of successful silica cover and TG on the surface of nanoparticles.
In the one hand, cube structure of nanoparticles of ZnFe2O4 and
branched structure of TG is observed obviously.
Fig. 5 shows the VSM pattern of ZnFe2O4 nanoparticle, ZnFe2O4/
SiO2 and ZnFe2O4/SiO2/TG nanocomposite. Investigation of VSM pat-
terns ZnFe2O4 nanoparticle (Fig. 5-a) shows this nanoparticle at room
temperature has paramagnetic behavior and can be separated easily
with an external magnet. Amount of saturated magnetism for ZnFe2O4
nanoparticle equals 19.325 emu/g, and its forcing is 4.98 G. After
modifying the surface of the ZnFe2O4 nanoparticles by SiO2, (Fig. 5-b),
yet these nanoparticles show paramagnetic behavior at the room
Fig. 4. TEM images of (a): ZnFe2O4 (b): ZnFe2O4/SiO2 (c): ZnFe2O4/SiO2/TG.
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Surfaces and Interfaces 14 (2019) 117–126
temperature and can be separated easily with an external magnet.
Amount of saturated magnetism for ZnFe2O4/SiO2 nanoparticle equals
15.363 emu/g. Amount of saturated magnetism of ZnFe2O4/SiO2/TG
nanocomposite equal 6.1657 emu/g (Fig. 5-c). However, in this nano-
composite reduced amounts of saturated magnetism but yet shows
paramagnetic behavior in the room temperature and can still be sepa-
rated easily with an external magnet.
Thermal stability of nanoparticles synthesized by coincidental study
of the chart (TGA/DTG) in a nitrogen atmosphere, at the environment
temperature up to 800° C was evaluated. Fig. 6 shows the TGA/DTG
pattern of ZnFe2O4 nanoparticle, ZnFe2O4/SiO2 and ZnFe2O4/SiO2/TG
nanocomposite. Investigation of thermal behavior of ZnFe2O4 nano-
particles (Fig. 6-a) shows 1.97% weight loss in one stage at 25–434 °C
which is due to the evaporation of water molecules and crystal structure
of ZnFe2O4 nanoparticles [33]. From the temperature of 434–800 °C
there is not much weight change that points to the presence of iron
oxide in this thermal range [16]. Investigating the thermal behavior of
ZnFe2O4/SiO2 nanoparticles Fig. 6b shows the weight loss is done in
two steps. The first stage of weight loss (1.45%) at temperatures ran-
ging from 25 to 155 °C, occurs due to surface evaporation of nano-
particles water [34]. This process is proved by the presence of the hot
forming pick at a temperature of 33.18 °C in DTG curve. The second
stage of weight loss of nanoparticle is observed by 1.25% of weight in
the temperature ranging from 155 to 450 °C, that due to effective water
evaporation and additional compounds [35] and it is confirmed in the
presence of hot forming pick at the temperature of 203 °C in DTG curve.
In the temperature ranging from 450 to 800 °C there was little weight
loss. The thermal behavior of ZnFe2O4/SiO2/TG nanocomposite Fig. 6c
shows that weight loss occurs in four stages. Initial weight loss in
temperature ranging from 25 to 193 °C by 3.2% is due to the loss of
water and methyl meta-acrylate and also remaining solution [36],
T. Etemadinia et al. Surfaces and Interfaces 14 (2019) 117–126

Fig. 5. VSM pattern of (a): ZnFe2O4 (b): ZnFe2O4/SiO2 (c): ZnFe2O4/SiO2/TG.

created hot forming pick in DTG curve at 51 °C, and confirms this. The
most weight loss in the second stage (22.37% of weight) was observed
in temperature ranging from 193 to 390 °C, due to decomposition of TG
links methyl meta acrylate [16,18]. The presence of hot forming pick in
the DTG curve at 257 °C confirms the above reason. The third stage of
weight loss, also is due to decomposition of TG branched structure by
4.55% in temperature ranging from 390 to 606 °C [18], that corre-
sponds to the presence of weak pick at 566 °C in DTG curve. In tem-
perature ranging from 606 to 800 °C, the fourth stage of weight loss is
observed in TGA chart with 10.43% weight loss. This is due to oxidation
of metal oxides [34], and this weight loss observed in the presence of
hot forming pick at 718 °C in DTG chart.
3.2. Effect of pH
pH is an important factor that affect the adsorption process by ef-
fecting the structure of pollutant and surface charge of the adsorbent
[37]. CR is an anion dye that is also used as an acid and base detector
[8], so when pH of dyed solution of CR is less than 4.71, its dye changes
to dark blue [4] and this causes to maximum frequency change, so that
in pH = 2.18–3.16 its maximum frequency (λmax) is 576 nm, and in
pH = 3.86 its maximum frequency is 567 nm [38], so alike with some
researchers studies investigation of CR dyed solution was done pH ≥ 5
[4,18,38–41]. Effect pH on congo red removal is shown in Fig. 7. With
increasing of pH from 5 to 11 decreases the efficiency of the CR re-
moval, so that the greatest extent of the removal in pH = 5 is more than

Fig. 6. TGA/DTG spectra of (a): ZnFe2O4 (b): ZnFe2O4/SiO2 (c): ZnFe2O4/SiO2/TG.

121
T. Etemadinia et al.
Fig. 7. The effect of pH on the performance of the CR removal using ZnFe2O4/
SiO2/TG (v = 50 mL, adsorbent mass 0.02 g, C0 = 10 mg/L, t = 60 min).
Fig. 8. pHzpc curve of ZnFe2O4/SiO2/TG (Volume of solution 50 mL, adsorbent
mass 0.025 g, time 24 h).
90%, due to pHzpc of adsorbent and anion structure of CR. pHzpc is one
of the parameters that are used in the adsorption process. pHzpc is one
of the most characteristics of adsorbent. In this study pHzpc ZnFe2O4/
SiO2/TG nanocomposite was determined 6.86 (Fig. 8). pHzpc is the in-
dicator of the point in which the surface charge of adsorbent is zero.
When pH ˂ pHzpc, then the surface charge of adsorbent matter has
positive charge and when pH ˃ pHzpc then the adsorbent matter has
negative charge, and when pH = pHzpc the surface of the adsorbent
matter is neutral (the number of the positive and negative charges is the
same) [37]. So, according to pH (pH ˂ pHzpc), dominant surface charge
in pHs less than pHzpc is positive. Thus, according to anion nature of the
CR, the electrostatic gravity force between adsorbent and pollutant
increases and yield of the removal and capacity of adsorption increases,
vice versa in pHs more than pHzpc the surface charge of the adsorbent is
negative and with increasing of the electrostatic repulsive force be-
tween the adsorbent and pollutant, removal yield, and capacity of ad-
sorption decreases. In other words, the yield increase with pH decline is
due to existing of protonated amine groups in acidic solutions, as a
result the positive charge of amine groups is absorbed by the negative
charge existing in –SO3- of anion dye of CR, and the efficiency of the
removal increases in low pH [18]. In other words, increasing the effi-
ciency and absorption capacity by decreasing the pH due to the pre-
sence of protichene amino groups in acidic solutions, thus the positive
charge of amino acid groups absorbed the negative charge in -SO3- CR
anionic and efficiency increases in the pH bottom [39].
The results of this study are similar to those of other scholars
[39–42]. Also, the study performed by Khaniabadi (2017) showed that
increasing of pH decreases efficiency [43].
3.3. Effect of contact time and initial congo red concentration
The effect of contact time on the extent of adsorption of CR in time
range from 5 to 180 min in pH = 5 and 50 mL of the solution of CR with
the adsorbent mass of 0.02 g in concentrations of 10, 20, 30, 40, 50, and
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Surfaces and Interfaces 14 (2019) 117–126
60 mg/L was tested (Fig. 9). According to the obtained results with
increasing of the initial concentration of the dye, the adsorption capa-
city increases. Also, with increasing of contact time to equilibrium time
in every concentration, the adsorption capacity increases, so that by
passing the time from 5 to 60 min the adsorption capacity increases and
after 60 min it follows almost a constant procedure. Then, the highest
adsorption capacity is related to the initial concentration of 60 mg/L
and contact time of 60 min. The reason of the increase in adsorption
capacity with increasing of the initial concentration of the dye is that in
such a condition the transfer force of mass increases, this phenomenon
overcomes resisting force against adsorption and causes to form con-
siderable extent of the thrust force to transfer pollutant from liquid
phase to liquid adsorbent joint surface [44]. The same procedure was
done in a study carried out by Ojedokun and Bello [45].
3.4. Effects of adsorbent dosage
Fig. 10 shows the effect of adsorbent dosage on the extent of ad-
sorption extent and efficiency of the removal of CR by ZnFe2O4/SiO2/
TG nanocomposite. As it is observed, with increasing of the mass of
adsorbent from 0.2 to 2 g/l, the extent of adsorption decreases and
reaches to 30 mg/L from 159.90 mg/L. Vice versa, the efficiency of the
removal of the CR increases by increasing the adsorbent dosage from
0.2 to 2 and reaches 100 from 53.3%. As it is demonstrated, with in-
creasing of adsorbent dosage the efficiency of the removal of CR in-
creases that is due to the increase of surface and availability of ad-
sorption sites [46]. On the one hand, with increasing of the adsorbent
dosage, the extent of the removal capacity of the CR decreases and this
is due to split in flux or gradient of the concentrate between the con-
centration of the dissolved mass in the solution and the concentration of
the dissolved mass on the adsorbent surface. So with increasing of the
adsorbent mass, the amount of absorbed dye in the solution on the unit
mass of the adsorbent decreases [47]. The obtained results in this study
correspond with the results of the research done by Khaniabadi et al.
(2017) about the removal of CR by active carbon obtained from Aleo-
vera and Montmurillonite [43,48].
3.5. Adsorption isotherms
The adsorption isotherm is one of the important factors in the
designation of the adsorption systems. Adsorption isotherm describes
the way of interactions between the adsorbent and the absorbed mass.
So, it is considered as the basic factor in the determination of the ad-
sorbent capacity and optimizing of the adsorbent usage. In this study,
we studied four isotherm models (Langmuir, Freundlich, Temkin,
Dubbin Radushkevich) of CR adsorption by ZnFe2O4/SiO2/TG nano-
composite. Fig. 11 shows the study of the isotherm models in the CR
adsorption by Zinc-ferrite modified by TG. According to the isotherm
charts and obtained results from Table 1, it was determined that from
four isotherm models, the equilibrium data of CR adsorption follow
Langmuir isotherm with a regression coefficient of R2 = 0.9912. This
fact that the laboratory data match Langmuir isotherm indicates the
adsorption of CR on the substrate of the ZnFe2O4/SiO2/TG nano-
composites is a monolayer. Also, it shows a homogenous distribution of
the active sites and the same energy on the surface of the adsorbent
[49]. RL which was obtained less than one indicates the adsorption
process by Longmuir model is suitable. The adsorption potential of the
CR (qmax) by ZnFe2O4/SiO2/TG nanocomposite based equals
128.205 mg/g. In this regard, the same results were achieved by Jiang
et al., Xiong et al., and Kim and Munagapati [50–52].
3.6. Adsorption kinetic
To achieve the information about the effective factors on reaction
speed, the evaluation of adsorption Kinetics is necessary. In this re-
search, we studied two kinetic models (pseudo-first order and pseudo-
T. Etemadinia et al. Surfaces and Interfaces 14 (2019) 117–126

Fig. 9. Effect of contact time and initial CR concentration using ZnFe2O4/SiO2/TG (pH = 5, v = 50 mL, adsorbent mass = 0.02 g).

second order). Studying the kinetics in different initial concentrations

of the absorbent matter (CR) was performed by ZnFe2O4/SiO2/TG na-
nocomposite (Figs. 12 and 13). The results obtained from the compar-
ison of amounts of R2 coefficient in two investigated kinetic models are
the indicator of the matching of CR adsorption process from the
equation of pseudo-second order. Also, according to the obtained re-
sults from Table 2 the adsorption capacity which was calculation by
kinetic equations (qe, cal) in the pseudo-second order kinetic model is
closer to the adsorption capacity of the adsorption tests (qe, exp), and
this is the confirm to the issue that the adsorption process follows
pseudo-second order kinetics. So, chemical adsorption is the restricting
stage of the process that is offered to evaluate the speed of the reaction.
According to the dominance of pseudo-second order kinetic, one can
Fig. 10. The effect of adsorbent dosage on the adsorption extent and the re-
say that the CR adsorption reaction on the surface of ZnFe2O4/SiO2/TG
moval of CR using ZnFe2O4/SiO2/TG (pH = 5, v = 50 mL, t = 90 min,
nanocomposite is done in two stages: the first stage is done fast, and the
C0 = 60 mg/L).
second is done slower and needs more time during the process [53]. The

Fig. 11. The investigation of isotherm models of CR adsorption using ZnFe2O4/SiO2/TG a: Langmuir, b: Freundlich, c: Temkin, d: Dubbin Radushkevich.

123
T. Etemadinia et al. Surfaces and Interfaces 14 (2019) 117–126

Table 1
Coefficients of isotherm models of CR adsorption using ZnFe2O4/SiO2/TG.
Models Isotherm constants Models Isotherm constants

Langmuir qmax (mg/g) 128.205 Temkin AT (L/mg) 2.05

KL (L/mg) 0.198 BT (j/mol) 27.59
RL 0.214 R2 0.988
R2 0.991
Ferundlich Kf 4.04 Dubinin–Radushkevich B (mol2/kj2) −2.8644
1/n 0.51 E (kj/ mol) 0.42
nF 1.95 R2 0.864
R2 0.699

Fig. 12. The application of the pseudo-first order kinetic model for CR adsorption using ZnFe2O4/SiO2/TG.

Fig. 13. The application of the pseudo-second order kinetic model for CR adsorption using ZnFe2O4/SiO2/TG.

Table 2
Kinetic constants for CR dye adsorption.
Pseudo-first order kinetic Pseudo-second order kinetic
C0 qe, exp K1 qe R2 K2 qe R2
mg/L mg/g 1/min mg/g g/mg.min mg/g

10 22.47 012.0 96 762 0.12 73.22 9967

20 43.46 008.0 93 65 2 10.43 9988
30 62.1 008.0 2.1 332 −02.0 48.58 9957
40 80.57 007.0 97 269 33 12.78 9995
50 89.43 016.0 26.1 654 5 91.9 9998
60 103.10 014.0 30.1 766 1 17.104 9998 Fig. 14. The effect of temperature on the adsorption process of CR using
ZnFe2O4/SiO2/TG (pH = 5, absorbent dosage = 0/2 g/l, solution volume
50 mL, initial concentration of the dye = 60 mg/L).
obtained results from this article correspond with the studies on the CR
removal by different adsorbents which were done in the years 2016 and
2017 [43,52,54].

3.7. Adsorption thermodynamics

Temperature, as an influential parameter in the determination of

the adsorption capacity, is one of the significant and the effective op-
tions in the physical and chemical processes of the adsorption. Fig. 14
shows the effect of the temperature on the adsorption capacity of the CR
by ZnFe2O4/SiO2/TG nanocomposite. According to the obtained re-
sults, by increasing the temperature from 15 to 45 °C the adsorption
capacity increases. These results perhaps are due to the increase in the
Fig. 15. The linear drawing of Lnkd versus 1/T for absorption of CR using
movements of CR molecules and increase of active sites for adsorption
ZnFe2O4/SiO2/TG.
with increasing of the temperature. Additionally, increasing the

124
T. Etemadinia et al.
Table 3
Thermodynamic parameters of adsorption of CR red using ZnFe2O4/SiO2/TG.
Temperature ΔG (KJ/mol) ΔH SΔ
(k) 288 298 308 318 KJ/mol J/mol
(k) (k) (k)
−3.8 −4.3 −5.1 −5.52 12.74 57.52
temperature decreases the movement of large dyed ions, so the in-
flammation effect causes large dyed molecules to penetrate into the
adsorbent. The results of this study correspond with the study by Mu-
nagapati on CR adsorption (2017) using Calcium Alergens [52].
To describe and confirm the mechanism of the CR adsorption by
ZnFe2O4/SiO2/TG nanocomposite, thermodynamic parameters such as
Gibbs free energy (ΔG), enthalpy (∆H), and entropy (∆S) were in-
vestigated (Fig. 15 and Table 3). As it is observed, Gibbs free energy is
negative in all temperatures and this shows the spontaneous of the
adsorption process. The numerical increase of the free energy by in-
creasing the temperature can identify the type of adsorption process
(physical or chemical). If the amount of the free energy is between 0 to
−20 KJ/mol, the adsorption process is physical. But, if it is between
−80 and −400 KJ/mol, the process is chemical. According to this
matter that less amount of free energy is less than −20 KJ/mol, so the
adsorption process is physical. The positive amount of enthalpy also
shows the adsorption reaction of CR on the ZnFe2O4/SiO2/TG nano-
composite is physical and endothermic. If ∆H˂25 KJ/mol, the adsorp-
tion reaction is physical and if ∆H ˃ 40 KJ/mol, the adsorption reaction
is chemical. Also, the positive amounts of the entropy show that the
efficiency of the absorbent and adsorbent randomly increase during the
process [52]. The studies by Taqui et al. are similar to the results of this
study [55,56]
4. Conclusion
In the present study, ZnFe2O4/SiO2/TG nanocomposite was syn-
thesized as a novel adsorbent and was identified using some techniques
such as VSM, TEM, XRD, FT-IR, and TGA. Then, the application of the
synthesized nanocomposite was investigated in removing of CR from
aqueous solutions. To achieve maximum adsorption capacity, effective
parameters on adsorption (pH, dye concentration, adsorbent dosage,
contact time, and temperature) were optimized. In the test optimized
conditions were pH = 5, contact time = 60 min, initial concentration of
the dye = 60 mg/L, absorbent dosage = 0.2 g/L, maximum adsorption
capacity = 159.90 mg/g. Consequently, four models of isotherms
(Langmuir, Freundlich, Temkin, Dubbin Radushkevich) in adsorption of
CR were investigated by identified. The results showed that test data
follow Langmuir isotherm. Additionally, two kinetic adsorption models
(Pseudo-first-order and Pseudo-second-order) were investigated by ki-
netic study in different initial concentrations from absorbed matter
(CR) by ZnFe2O4/SiO2/TG nanocomposite and the obtained results
showed that the test data follow the kinetic model of Pseudo-second-
order. To compare and demonstrate the efficiency of ZnFe2O4/SiO2/TG
nanocomposites in comparison with ZnFe2O4 nanoparticles and
ZnFe2O4/SiO2 nanoparticles, experiments were carried out under op-
timal conditions on ZnFe2O4 and ZnFe2O4/SiO2 adsorbents. In the op-
timum conditions of pH = 5, contact time = 60 min, initial dye con-
centration = 60 mg/L, and adsorbent dose = 0.2 g/L, The maximum
absorption capacity for each of the ZnFe2O4 and ZnFe2O4/SiO2 ad-
sorbents was equal to 49.37 and 75.227 mg.g. As the results showed,
with the correction of the ZnFe2O4 surface with TG, the absorption
capacity increased significantly, which indicates the high efficiency of
the ZnFe2O4/SiO2/TG nanocomposite in the removal of the CR dye. As
a result, according to the high capacity of adsorption of this stable,
environment lover, and low-cost nanocomposite in the removal of the
dye, and availability of initial materials, and biocompatibility of it, we
125
Surfaces and Interfaces 14 (2019) 117–126
can use it as an effective and efficient absorbent in the removal of dye.
Conflict of interest
The authors declare that there is no conflict of interest
Acknowledgments
The authors are thankful to the Birjand University of Medical
Sciences for technical and financial support.
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