Journal of Dispersion Science and Technology

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Using zeolite and Fe3O4@zeolite composites in

removal of Reactive Red 120 from wastewater:
Isotherm, kinetic, thermodynamic and adsorption
behaviors

Çiğdem Ay & Zeynep Sarpaşar

To cite this article: Çiğdem Ay & Zeynep Sarpaşar (2022): Using zeolite and Fe3O4@zeolite
composites in removal of Reactive Red 120 from wastewater: Isotherm, kinetic, thermodynamic
and adsorption behaviors, Journal of Dispersion Science and Technology, DOI:
10.1080/01932691.2022.2135520

To link to this article: https://doi.org/10.1080/01932691.2022.2135520

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JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/01932691.2022.2135520

Using zeolite and Fe3O4@zeolite composites in removal of Reactive Red 120

from wastewater: Isotherm, kinetic, thermodynamic and adsorption behaviors
 dem Ay
Çig and Zeynep Sarpaşar
Department of Chemistry, Ku€tahya Dumlupınar University, Science and Art Faculty, K€utahya, Turkey

ABSTRACT ARTICLE HISTORY

It is a well-known fact that the release and dispersion of complex organic dyestuffs into the envir- Received 23 March 2022
onment adversely affect human health and other living organisms. Due to industrial activities, pol- Accepted 9 October 2022
lution of water resources, which are vital for living organisms, is one of the most critical
KEYWORDS
environmental problems nowadays. It is essential to remove the pollutants before they are dis-
Adsorption; Iron Oxide;
charged into the environment to eliminate environmental damage. In this study for the removal Reactive Red 120; Zeolite
of Reactive Red 120 (RR120) dyestuff from an aqueous solution, we employed natural zeolite and
iron oxide-zeolite (Fe3O4@Z) as adsorbents. The adsorbents were characterized by Fourier trans-
form infrared spectroscopy, X-ray diffractometry, X-ray fluorescence spectrometry, Scanning elec-
tron microscopy energy dispersive X-ray spectroscopy, and Brunauer–Emmett–Teller analysis. The
effects of parameters such as pH, contact time, and temperature on RR120 adsorption were also
investigated. In addition, the adsorption equilibrium was analyzed with kinetic, isotherm, and
thermodynamic parameters. It was found that the adsorption of RR120 on natural zeolite and
Fe3O4@Z followed the Langmuir and Freundlich isotherm, respectively, and the adsorption process
for both adsorbents proceeded spontaneously (DG8<0) and exothermic (DH8<0) with a pseudo-
second-order kinetic model. Zeolite and Fe3O4@Z adsorption capacities for RR120 were 145.9 and
154.3 mg/g at 20
C, respectively. It was determined that no significant matrix effect occurs in
adsorption with synthetic wastewater prepared to evaluate the potential performance of adsorb-
ents. According to the results obtained, Fe3O4@Z composite was found more effective adsorbent
than natural zeolite for RR120 removal.

GRAPHICAL ABSTRACT

1. Introduction structures.[5,6] Wastewaters released to lakes or water sour-

The release of dyestuff wastes used in industry (textile, lea-
ther, paper, food processing, etc.) into seas, lakes, and
underground waters has become an important problem for
public health.[1–3] Today, approximately 280,000 tons/year of
dyes used in the world textile industry are discharged into
the environment as waste.[4] These wastewaters contain par-
asites, pathogens, heavy metals, and organic compounds
resistant to degradation due to their complex chemical
ces use the dissolved oxygen in the water, causing the con-
centration to decrease and the ecological balance of the
system to deteriorate.
Reactive dyes from azo dyes exhibit chemical structures
based on aromatic and heterocyclic groups containing
–N¼N– and –C¼N– bonds.[7] Reactive dyes that bind to
cotton and cellulose fibers by covalent bonds constitute the
most significant dyes used in textile processing.[8] In

dem Ay
CONTACT Çig cigdem.ay@dpu.edu.tr Department of Chemistry, K€ utahya Dumlupınar University, 43100 K€
utahya, Turkey
Supplemental data for this article can be accessed online at https://doi.org/10.1080/01932691.2022.2135520
ß 2022 Taylor & Francis Group, LLC
2 Ç. AY AND Z. SARPAŞAR
Figure 1. XRD pattern for Fe3O4, Zeolite and Fe3O4@Z (a) and FT-IR Spectra of
Zeolite and Fe3O4@Z (b).
addition, it is frequently used in the textile industry due to
its advantages, such as solubility in water, easy application,
bright colors, and stable coloring.[9] Their high solubility
causes the presence of excess dyestuffs in wastewater. It is
estimated that about 10–60% of reactive dyes are lost during
dyeing.[10–13] Although their high resistance to chemical,
photochemical and biological degradation is an industrial
advantage, they cause persistence in the waste environment.
This coloration in the waters harms the aquatic ecosystem
as it prevents the entry of sun rays and photosynthetic activ-
ity and changes the solubility of gases in water. For this rea-
son, it is necessary to eliminate the pollution and reduce its
effect before industrial wastewater is released into the
environment.
Removal of organic and inorganic pollutants in water/
wastewater is critical due to the depletion in water resources.
Recycling and disposal of industrial wastes without harming
the ecosystem is now possible with the new cleaning tech-
nologies. These methods should be inexpensive, highly
applicable, and suitable for different types of waste. Many
different methods such as membrane filtration,[14] chemical
oxidation,[15] solvent extraction,[16] adsorption/biosorp-
tion,[17,18] coagulation,[19] ion exchange,[20] electrochemical
reduction[21] are used for waste removal up to date. These
techniques include adsorption; it is the most widely used
because of its easy, clean, and waste-free operation. When
choosing the adsorbents to be used in the adsorption pro-
cess, abundant and cost-effective adsorbents are preferred.
Examples of these adsorbents are activated carbon,[22] zeo-
lite,[13,23] agricultural waste,[24–26] plant fibers,[27] and clays.
[28–30]
In recent years, zeolite has been widely used to
remove wastewater. The mineral class of “tectosilicates”
includes zeolites, which are naturally occurring, hydrated
aluminosilicate minerals with crystalline microporous struc-
tures.[31] In zeolites, which have a three-dimensional alu-
minosilicate structure, Si(IV) is in the form of Al(III). [32]
Because they are inexpensive, natural zeolites like clinoptilo-
lite, mordenite, and phillipsite have drawn much interest as
suitable adsorbents for wastewater treatment. Especially cli-
noptilolite, which is among the natural zeolite species, is fre-
quently preferred due to its superior ion exchange and
adsorption properties. Clinoptilolite is the most abundant
zeolite mineral as a reserve in Turkey.[33] Therefore, zeolite
was preferred as an adsorbent in this study because it is eas-
ily available, inexpensive, nontoxic, insoluble in water, has a
large surface area, and contains functional groups that can
interact with adsorbates.
In recent years, zeolite-based composites have been devel-
oped to remove environmental pollution. The fact that these
developed zeolites/composites have better physicochemical
stability, easier reusability, and higher adsorption capacity
than natural zeolites has led researchers to show more inter-
est in zeolites/composites.[1] While obtaining the composites,
it was aimed to improve the stability and adsorption capaci-
ties of inorganic and polymeric adsorbents, and zeolites
were used as support/fill material.[34] Senguttuvan et al.
examined the potential of polypyrrole/zeolite composite for
adsorption of Reactive blue (RB) and Reactive Red (RR).
The maximum adsorption capacity of RB and RR using the
zeolite composite was 122.32 and 116.53 mg/g, respect-
ively.[35] In the zeolite/reduced graphene oxide composite
study, the maximum removal efficiency for methylene blue
was found at 98.5%.[36] Magnetic nanoparticles have been
suggested as adsorbents for separating various contaminants
from water sources due to their large specific surface area
and ease of separation under an external magnetic
field.[32,37] Small particle size, high magnetic response, and
the surface performance of functional groups are just a few
of the exceptional qualities and traits of magnetic iron oxide
nanoparticles (Fe3O4) that make them ideal for separating
and extracting highly harmful organic contaminants from
water and wastewater.[32,38] It has been noted recently that
adsorbents made using Fe3O4 effectively remove both
organic and inorganic pollutants from wastewater. In this
study, Alves et al. examined the performance of citric acid-
doped polyaniline and magnetic iron oxide (MOM) hybrids
in the adsorption/photodegradation of blue methylene dye
(MB) in the aqueous medium.[39] Fe3O4 carbon nanocompo-
site prepared by coprecipitation and hydrothermal method
was used in As(V) removal. It was reported that the nano-
composite, which is also very successful in removing inor-
ganic impurities, exhibits excellent success in As(V)
adsorption.[40]
 JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 3

In the study, natural zeolite was used without any pre-
treatment to remove Reactive Red 120 (RR120), and a com-
posite adsorbent (Fe3O4@Z) was prepared with iron oxide
nanoparticles. The prepared Fe3O4@Z and natural zeolite
adsorption processes were examined with different parame-
ters, kinetic, isotherm, and thermodynamic data were
obtained, and their adsorption capacities were compared.
2. Materials and methods
2.1. The solution of Reactive Red 120 (RR120)
All chemicals used are of analytical purity, and Reactive Red
120 (RR120) dyestuff was obtained from Dystar company.
500 mg/L stock dye solution was prepared by dissolving
RR120 in deionized water, and dyestuff solutions were
diluted at desired concentrations from the stock. The
molecular structure and some physical properties of RR120
dyestuff are given in Figure S1 and Table S1, respectively.
2.2. Preparation of magnetic adsorbent
The zeolite obtained from the Şaphane region of K€ utahya
was first dried in an oven, ground, and sieved through a
150 mm sieve. The prepared zeolite was dried at 80
C for
12 hours. Then, 5.0 g of zeolite was dispersed in 100 mL of
deionized water for 5 minutes with a magnetic stirrer. 3.0 g
of FeCl3.6H2O and 2.36 g of FeSO4.7H2O were added with a
ratio of Fe(III)/Fe(II) of 2:1 and mixed for 30 minutes in a
nitrogen environment. Then, NaOH solution slowly was
added so that the pH was between 10 and 12, and stirring
was continued for one h in a nitrogen environment. The
obtained Fe3O4 zeolite (Fe3O4@Z) was collected with a mag-
net and washed three times with deionized water. To pre-
vent the oxidation of the nanoparticles during the drying
stage, freeze-drying was applied. Fe3O4@Z was frozen in
liquid nitrogen and dried under a vacuum of 0.107 mbar
and in a device set at 57
C (Telstar Cryodos, Spain).
Table 1. BET analysis results of Zeolite and Fe3O4@Z.
Surface Total pore
area m2/g volume (cm3/g)
Zeolite 5.838 ± 0.010 0.138 ± 0.004
Fe3O4@Z 7.168 ± 0.008 0.213 ± 0.011
2.3. Characterization of the natural zeolite and Fe3O4@Z
Functional groups in zeolite and Fe3O4@Z structures were
investigated by Fourier transform infrared (FTIR, Bruker,
Germany) spectroscopy method. For the FTIR spectra, pel-
lets were prepared with KBr and studied in the range of
400–4000 cm˗1. Crystal structures of Zeolite and Fe3O4@Z
are determined by X-ray diffractometry (XRD, Rigaku Mini-
Flex, Japan), morphological structures, and nanoparticle
sizes are determined by scanning electron microscopy
energy dispersive X-ray spectroscopy (FE-SEM-EDX,
QUANTA 400F Field Emission Scanning Electron
Microscope, USA) and specific surface area, pore volume,
pore size was performed by Brunauer–Emmett–Teller
Analysis (BET, Quantachrome Instruments, USA). X-ray
fluorescence spectrometry (XRF, Panalytical Axios MAX,
Netherlands) was used for elemental composition research.
2.4. Adsorption experiments
Optimization of system conditions in adsorption experi-
ments is significant for dye removal efficiency. Therefore,
kinetic and isotherm studies were carried out after deter-
mining the appropriate removal conditions in the study.
pH (1.50–6.50), initial concentration (25–150 mg/L), and
contact time (5–120 min) experiments were carried out to
determine the appropriate parameters with the highest
adsorption capacity in the adsorption of RR120 on zeolite
and Fe3O4@Z. 50.0 mL of RR120 solution with a concentra-
tion of 50.0 mg/L was taken, 0.01 g of adsorbents were added
and mixed at 500 rpm. Various concentrations of hydro-
chloric acid (HCl) and sodium hydroxide (NaOH) solutions
were used to adjust the initial pH values of the solutions,
and pH measurements were measured with a pH meter
(Metler Toledo Seven Easy). After stirring for an hour, the
adsorbents were filtered off the dye solution. The absorbance
values of the solutions were measured in UV–Vis spectrom-
etry (Shimadzu UV-2550, Japan) at a wavelength of 517 nm.
Kinetic and isotherm experiments were carried out at differ-
ent temperatures (20, 30, 40, and 50
C) at the pH values
determined for the adsorption of RR120 on zeolite and
Fe3O4@Z. The parameters calculated from the results
obtained from the experiments and the effects of adsorbents
Average pore on RR120 removal were compared.
size (nm) The adsorption capacity (mg/g) and adsorption percent
47.38 ± 0.05 for the adsorption of RR120 on zeolite and Fe3O4@Z were
59.48 ± 0.04
calculated using Equations (1) and (2).

Table 2. Kinetic parameters for RR120 adsorption onto Zeolite and Fe3O4@Z.
Pseudo-first-order Pseudo-second-order
q (mg/g) k1 q1 k2 qe
experimental t (
C) (min1) (mg/g) r12 (g/mgmin) (mg/g) r22
2 2
Zeolite 86.32 ± 0.08 20 3.25  10 5.80 0.797 1.38  10 87.11 0.999
84.54 ± 0.23 30 2.99  102 4.90 0.706 1.86  102 85.09 0.999
81.22 ± 0.12 40 2.83  102 3.03 0.544 2.36  102 81.66 0.999
78.38 ± 0.26 50 1.74  102 2.78 0.462 2.66  102 78.89 0.999
Fe3O4@Z 100.4 ± 0.2 20 2.66  102 3.01 0.677 2.58  102 100.9 0.999
97.67 ± 0.11 30 2.94  102 3.07 0.826 3.00  102 98.04 0.999
95.58 ± 0.21 40 2.19  102 1.96 0.618 5.27  102 95.86 0.999
93.29 ± 0.23 50 1.50  102 1.57 0.448 8.82  102 93.41 0.999
4 Ç. AY AND Z. SARPAŞAR

Table 3. Isotherm parameters for RR120 adsorption onto zeolite and Fe3O4@Z.
Langmuir Freundlich Dubinin–Radushkevich (D–R)
t KL qm KF qm b E
(
C) (L/mg) (mg/g) RL2 n (L/g) R F2 (mol/g) (mol2/kJ2) RD-R2 (kJ/mol)
Zeolite 20 3.25  102 145.9 0.996 2.38 16.42 0.969 7.27  102 3.40  106 0.978 12.12
30 3.12  102 127.9 0.997 2.47 15.42 0.953 6.23  102 3.31  106 0.935 12.29
40 3.04  102 126.0 0.999 2.35 13.36 0.970 6.32  102 3.47  106 0.978 12.00
50 2.67  102 119.8 0.997 2.30 11.66 0.990 6.00  102 3.54  106 0.993 11.88
Fe3O4@Z 20 4.18  102 154.3 0.986 3.08 27.82 0.996 5.10  102 2.59  106 0.995 13.89
30 4.00  102 145.5 0.983 3.09 26.03 0.993 4.74  102 2.42  106 0.991 14.37
40 4.08  102 135.9 0.991 3.05 23.97 0.995 4.59  102 2.31  106 0.996 14.70
50 4.05  102 123.2 0.989 3.14 22.56 0.996 4.00  102 2.12  106 0.996 15.37

ðC0  Ct Þ V
qt ¼
m Fe3O4@Z, in addition to the characteristic peaks of the zeo-
C0  Ct
Adsorption % ¼  100
C0
where qt (mg/g) is the adsorbed amount of RR120 per gram
of adsorbent at any time t; C0 and Ct (mg/L) are the con-
centrations of RR120 in the initial solution and at any time
t, respectively. V (L) is the volume of the solution, and m
(g) is the weight of the adsorbent. Each experiment was car-
ried out three times, and the results’ standard deviations
were calculated using a 95% confidence level.
2.5. Application in synthetic wastewater
To examine the effects of wastewater components on RR120
adsorption, the synthetic wastewater medium given in Table S2
was created.[41] 50.0 mL of the prepared synthetic wastewater
was taken and added with 0.01 g of zeolite and Fe3O4@Z each.
The medium was adjusted to the appropriate pH and mixed at
20
C at 500 rpm for one hour, and the adsorption yield of
RR120 in the wastewater medium was investigated.
3. Results and discussion
3.1. Characterization of adsorbents
The results of the chemical analysis performed with the zeolite
XRF device are given in Table S3. With the Si/Al or SiO2/
Al2O3 molar ratio of the zeolites, which are very rich in silica,
hydrophobicity and acid resistance increase.[42] According to
the Si/Al molar ratio, they are classified as low silica zeolite
(Si/Al  2), intermediate silica zeolite (2＜Si/Al＜5), and high
silica zeolite (Si/Al  5). In general, high silica zeolites are
used for removing organic pollutants due to their high hydro-
phobicity.[42] In addition, boles defined the natural zeolite as
clinoptilolite if the Si/Al ratio is greater than 4.[33,43] The Si/Al
ratio of 5.02 in this study showed that the natural zeolite was
a silica-rich clinoptilolite, and other characterization studies
supported the results. Besides, the loss on ignition of natural
zeolite at 500
C was found to be 14.35%.
The XRD analyses performed to examine the mineral-
ogical and crystallographic structure of adsorbents are given
in Figure 1a. When the XRD pattern of zeolite was exam-
ined, it was found that it contained clinoptilolite as the
main mineral and consisted of some quartz.[44] The peaks of
the amorphous structure of clinoptilolite are seen at 22.53
,
30.23
, 37.18
, 38.45
, and 46.58
. In the XRD pattern for
(1)
lite, diffraction peaks (220), (311), (400), (511), and (440)
(2) characterizing the cubic spinel crystalline structure of Fe3O4
were observed. These peaks are compatible with magnetite
phase standard data.[45] FTIR analysis was used to provide
structural knowledge about functional groups of samples.
FTIR spectra of zeolite and Fe3O4@Z are given in Figure 1b.
The peak at 1054 cm1 is due to Si–O(Si) ve Si–O(Al) asym-
metric stretching vibrations. Symmetric stretching vibrations
of Si–O-Si ve Si–O–Al are observed at 717 cm1 and
606 cm1, respectively, and O–Si–O bending vibrations at
452 cm1.[46] According to Figure 1b, The direction of the
majority of the bands has not changed significantly, indicat-
ing that the crystalline structure of zeolite has been pre-
served since it was magnetized.[47] The stretch vibration
bands of the water molecule adsorbed on the surface were
observed between 3618 and 3195 cm1 and the deformation
vibration band at 1633 cm1.[47,48] The characteristic Fe–O
band (590–610 cm1) with Fe3O4@Z is masked due to the
symmetrical stretching vibrations of Si–O–Al. The results
show that the Fe3O4@Z composite was successfully formed
from zeolite and Fe3O4 nanoparticles.
The two main factors affecting adsorbents’ performance
in the adsorption process are specific surface area and total
pore volume.[49] The BET technique analyzed the surface
areas, pore volume, and pore diameters of zeolite and
Fe3O4@Z adsorbents, and the results are listed in Table 1.
The surface area, pore volume, and pore size of Fe3O4@Z
adsorbent were higher than zeolite, thus providing more
adsorption sites for RR120 adsorption on Fe3O4@Z surface
and sufficiently large pore volume for RR120.[50]
In order to determine the surface morphology of the
adsorbents, the dried samples were placed on a 200 Å thick
carbon band, and SEM/EDX analyzes were taken by making
point focusing. The crystals in the layered structure seen
from the SEM image of the zeolite (Figure 2a) show the cli-
noptilolite mineral. In addition, mineral peaks belonging to
the zeolite content are observed in the EDX analysis (Figure
2d). Examination of the SEM images of Fe3O4@Z (Figure
2b) also showed that the placement of Fe3O4 nanoparticles
resulted in changes in the structure of the zeolite. In add-
ition, in the SEM image taken by the backscattering method
(BSED) (Figure 2c), it is seen that the regions where the
nanoparticles are concentrated have clear contrast. In the
EDX analyzes (Figure 2e) taken from these regions, it was
observed that the iron ratio was relatively high.

Figure 2. SEM image of zeolite (a), SEM image of Fe3O4@Z (b), BSED image of Fe3O4@Z (c), EDX analysis of zeolite (d), and EDX analysis of Fe3O4@Z (e).
Figure 3. Effect of pH on the adsorption of RR120 onto Zeolite and Fe3O4@Z.
3.2. Effect of pH
It is known that the pH of the adsorption medium can
affect the surface charge of the adsorbent, the degree of ion-
ization of different pollutants, the separation of functional
groups in the active sites of the adsorbent, and the molecular
structure of the dyestuff. Therefore, solution pH is an import-
ant parameter in adsorption since it affects both the aqueous
chemistry and surface binding sites of the adsorbent.[51]
Figure 3 shows the effect of pH of RR120 adsorption on
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 5
zeolite and Fe3O4@Z. It was observed that adsorption
decreased with increasing pH for both adsorbents. The
decreased number of positively charged regions on the adsorb-
ent at high pH causes strong electrostatic repulsion between
the adsorbate and the adsorbent.[52] In studies with similar
results, it has been reported that low adsorption of reactive
dyes in alkaline environments is due to deprotonation of sur-
face groups, which leads to electrostatic repulsion between the
negatively charged regions of the adsorbent and anionic
dyes.[45,52,53] Zeolite and Fe3O4@Z surfaces protonated at low
pH values have become attractive for RR120 adsorption. Thus,
hydrogen bonding and van der Waals interactions can be
observed between the adsorbent surfaces and the dye mole-
cules. In the experiments carried out, the maximum amount
of adsorbed dyestuff was reached at pH 1.50, and it was found
to be 95.96 ± 0.54 mg/g and 136.2 ± 0.6 mg/g for zeolite and
Fe3O4@Z, respectively. Patra et al.,[54] Zhou et al.[55] and
Temesgen et al.[56] reported optimum pH values for the
adsorption of reactive dyes as 3.0, 3.0, and 4.0, respectively.
This study was carried out in a much more acidic medium
due to the anionic groups’ density on the adsorbents’ surface.
3.3. Effect of temperature and contact time
The adsorption capacity of RR120 removed by zeolite and
Fe3O4@Z versus contact time is illustrated in Figure 4. This
figure shows that most of the adsorption on the zeolite takes
place within the first 30 minutes, and the adsorption rate
6 Ç. AY AND Z. SARPAŞAR
Figure 4. Effect of contact time for the adsorption of RR120 onto Zeolite (a) and Fe3O4@Z (b), Pseudo-second-order kinetic plots for RR120 adsorption onto Zeolite
(c) and Fe3O4@Z (d) at various temperatures.
increases with the increase in temperature, where the time
for the adsorption process to reach equilibrium was found
to be 50 minutes at 20
C and 30 minutes at 50
C. Similarly,
the time to reach the equilibrium of RR120 adsorption on
Fe3O4@Z (Figure 4b) decreased with increasing temperature.
However, the amount of dyestuff adsorbed on the surface
decreased with increasing temperature for both adsorbents.
In the experimental results, the amount of RR120 adsorbed
at 20
C was found to be 86.32 ± 0.08 mg/g and
100.4 ± 0.2 mg/g for zeolite and Fe3O4@Z, respectively. These
values decreased to 78.38 ± 0.26 mg/g for zeolite and
93.29 ± 0.23 mg/g for Fe3O4@Z at 50
C, indicating that an
exothermic and physical adsorption process controls RR120
adsorption. In addition, both the adsorption capacity and
the rate of the adsorption process increased with the Fe3O4
nanoparticle composite. In the study of Ciobanu et al.,[53]
the adsorption of Reactive Blue 19 dyes onto uncalcined and
calcined nanohydroxyapatite was investigated. While main-
taining the other parameters (pH ¼ 3, adsorbent dosage
2 g/L, initial dye concentration 65 mg/L, and contact time
3 hours) constant, the influence of temperature on the dye
adsorption on nanohydroxyapatite samples was investigated
at three different temperatures (20, 40, and 60
C). It was
reported that the adsorption capacity decreased with the
increase in temperature, so the exothermic process
controlled the Reactive Blue 19 dye adsorption. When the
research on the adsorption of reactive dyes was examined, it
was observed that the contact time of the adsorption could
vary from 10 minutes to 9 days. [57] In this study, the
adsorption reached equilibrium in 30–50 minutes, showing
that the adsorption process was completed quickly and
effectively. These results support that adsorption is a fast,
easy-to-apply and, alternative method for dye removal.
3.4. Kinetics of RR120 adsorption
Adsorption kinetics, which shows the time-dependent change
of the adsorption process, is an important parameter in under-
standing the mechanism. In this study, dynamic experimental
data were analyzed with first-order and pseudo-second-order
kinetic models to determine the kinetic behavior of RR120
adsorption.[58] The equations of the models are given below;
pseudo-first-order kinetic model[59]
lnðqe  qt Þ ¼ lnqe  k1 t (3)
pseudo-second-order kinetic model[60]
t 1 1
¼ þ t (4)
qt q2e k2 qe
where k1 (1/min) and k2 (g/mg min) are pseudo-first-order and
 JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 7

Figure 5. Adsorption isotherms of RR120 onto zeolite (a) and Fe3O4@Z (b); Langmuir isotherm of zeolite (c); Freundlich isotherm of Fe3O4@Z (d) at various
temperatures.

pseudo-second-order rate constants, respectively. qe and qt 3.5. Isotherms of RR120 adsorption

(mg/g) are amounts of RR120 adsorbed at equilibrium and at
The dynamic equilibrium between the adsorbate collected on
time t. Values of k2 and qe were calculated from the plot of
the surface during adsorption and the adsorbate remaining in
t/qt versus t (Figure 4c and d). All of the kinetic parameters of
the solution is investigated by adsorption isotherms.[61]
RR120 at various temperatures are given in Table 2. The correl-
Isotherms are generally obtained by reaching the equilibrium
ation coefficient (r22) values, which were 0.999 at all studied
of adsorbate solutions at different concentrations with a certain
temperatures, obtained for the pseudo-second-order kinetic
amount of adsorbent. Isotherms, which are essential in explain-
model for both adsorbents were found to be high. Besides, the
ing the adsorption process, are expressed mathematically with
increase in the rate constants (k2) calculated according to the
equations. In the present study, the RR120 adsorption was ana-
pseudo-second-order kinetic model of the adsorption of RR120
lyzed by Langmuir,[62] Freundlich,[63] Dubinin–Radushkevich
with the increase in temperature shows that the adsorption pro-
(D–R),[64] Redlich–Peterson65 isotherm models.
cess comes to equilibrium rapidly. Adsorption capacity

decreased with increasing temperature, indicating that RR120 qm KL Ce
qe ¼ (5)
adsorption is fast at low temperatures and more effective at 1 þ KL Ce
high temperatures. This effect can be interpreted by assuming

1
that due to the increase in the total energy of the adsorbate at RL ¼ (6)
higher temperatures, the escaping tendencies also increase; thus, 1 þ KL C0
the adsorption of the adsorbate species decreased.[41] RR120
qe ¼ KF : Ce1=n (7)
adsorption process onto zeolite and Fe3O4@Z proceeds with
low-temperature physical adsorption mechanism. As a result, qe ¼ qm : exp ðb:e2 Þ (8)
the qe values calculated at all studied temperatures are very

1
close to the experimentally found q values in equilibrium, indi- e ¼ RT : ln 1 þ (9)
cating that the adsorption kinetics is pseudo-second-order. Ce
8 Ç. AY AND Z. SARPAŞAR
Table 4. Thermodynamic parameters of the RR120 adsorption onto zeolite
and Fe3O4@Z.
t DSo
(
C) DGo (kJ/mol) (J/mol K)
Zeolite 20 2.39
30 2.34 4.86
40 2.29
50 2.24
Fe3O4@Z 20 2.96
30 2.95
40 2.93 1.17
50 2.92
1
E ¼ pffiffiffiffiffi
2b


Ce 1 1
¼ þ 0 Cea
qe bRP q0m qm
where C0 and Ce (mg/L) are the initial and equilibrium con-
centrations of RR120, qe, and qm (mg/g) are the equilibrium
and maximum adsorption capacity. KL (L/mg) is called the
Langmuir constant depending on temperature and adsorp-
tion enthalpy, RL (dimensionless) separation factor, or equi-
librium parameter.[66] KF (L/g) and n are Freundlich
isotherm constants. KDR (mol2/kJ2) and eDR (kJ/mol) are
constant, and the Polanyi potential of the DR isotherm
model, respectively. Freundlich and Langmuir isotherms are
combined to create the Redlich-Peterson model, which has
three parameters.[65,67] bRP (L/mg) is the constant of the
Redlich-Peterson model and a is exponent, which can be
varied from 0 to 1. When the b 1q0 value tends to zero, the
RP m
Redlich-Peterson model approaches the Freundlich model,
whereas when the a value tends to one at low concentra-
tions, it approaches the Langmuir model.
The adsorption isotherms obtained by working with dye-
stuff concentrations in the range of 25–150 mg/L are given
in Figure 5. Adsorption capacities in experiments performed
at different temperatures were calculated using Equation (1).
It was observed that the adsorption of RR120 on zeolite and
Fe3O4@Z increased with the initial dye concentration. When
Figure 5a is examined, it is observed that the amount of
adsorbed RR120 generally increases with the increase in
concentration; however, the amount of adsorbed material at
high concentrations does not change much with increasing
concentration. The RL values calculated from Equation (6)
were found less than unity at all temperatures, so the
adsorption of RR120 onto both adsorbents is favorable at all
studied temperatures. Moreover, it is observed that the
amount of adsorbed RR120 increases with an increase in
concentration at the adsorption of RR120 onto Fe3O4@Z
(Figure 5b). This isotherm shape shows multilayer adsorp-
tion, namely the Freundlich isotherm, in which each mol-
ecule adsorbed in each layer provides space for the
adsorption of molecules in the next layer. The graphs drawn
according to the isotherm models are shown in Figure 5c
and d; the parameters calculated from the graphs are pre-
sented in Table 3. According to the estimated correlation
coefficient values for the isotherm models, the adsorption of
RR120 on zeolite and the adsorption of RR120 on Fe3O4@Z
are compatible with the Langmuir (Figure 5c, RL2) and the
Freundlich (Figure 5d, RF2) isotherm models, respectively.
Moreover, the value of n (Freundlich constant) indicates the
DHo
(kJ/mol)
favorability of adsorption. Values of n > 1 represent the
favorable nature of adsorption; accordingly, RR120 is favor-
3.81 ably adsorbed by zeolite and Fe3O4@Z at all studied temper-
atures (see Table 3). Similar to findings, Toor and Jin
showed that for the adsorption of congo red from waste-
3.30 water on modified natural bentonit, the best-fit adsorption
isotherm model was Freundlich.[68] According to Peyghami
et al., the equilibrium data for the adsorption of Basic violet
16 from aqueous solutions by zeolite/Fe3O4 nanocoposite
(10) was best fitted by the Freundlich isotherm.[47]
In the DR isotherm model (Figure S2), frequently used
when describing physical or chemical adsorption processes,
(11)
the pore structure of adsorbents with heterogeneous surfaces
is considered. According to the internal free energy (E)
value, physical adsorption occurs in the 8–16 kJ/mol range,
while chemical adsorption occurs in the 20–40 kJ/mol
range.[69,70] The values of E in the present case are found to
be between 8 and 16 kJ/mol (Table 3), corresponding to
physical adsorption at all studied temperatures.
The isotherm parameters of the Redlich-Peterson model
are presented in Table S4, and the results are shown in
Figure S3. a values for zeolite and Fe3O4@Z were deter-
mined as 0.98 and 0.64, respectively. The a value approach-
ing 1.0 brought the Redlich-Peterson isotherm closer to
Langmuir. The a value is less than 1.0, and the bRP value is
more significant, bringing the b 1q0 value closer to zero, fit-
RP m
ting this isotherm to the Freundlich isotherm.
3.6. Estimation of the thermodynamic parameters for
RR120 adsorption
Thermodynamic parameters of the adsorption of RR120
onto zeolite and Fe3O4@Z, standard free energy change
(DGo), free enthalpy change (DHo) and free entropy change
(DSo), were determined using the following equations;
DGo ¼  RT lnK L (8)
DSo DH o
lnKL ¼  (9)
R RT
DHo and DSo values were calculated from the lnKL 1/T
plot and DGo values for all temperatures were found using
Equation (11). A negative DGo value indicates that adsorption
occurs spontaneously (Table 4). Also, the value that decreases
with the increase in temperature indicates that it is inclined to
low temperature.[71] Similarly, the negative values of DHo show
the exothermic nature of RR120 adsorption. The DSo values
calculated for zeolite and Fe3O4@Z were found 4.86 and
1.17 (J/mol K), respectively. These negative values in the
entropy change indicate that the regularity of the molecules
increases during adsorption. Similar thermodynamic data in
dye adsorption was also reported by Haghighizadeh et al.[72]
Muhammad et al.[73] and Kamranifar and Naghizadeh.[74]

3.7. Studies of synthetic wastewater
Experiments were performed under optimum adsorption con-
ditions to evaluate the potential performance of adsorbents in
the removal of RR120 from wastewater. In synthetic waste-
water experiments carried out at 20
C, the adsorbed amount
of RR120 was found 86.32 ± 0.08 and 100.4 ± 0.2 mg/g for
Zeolite and Fe3O4@Z, respectively. These values are very close
to the experimentally found q values (82.46 ± 0.12 mg/g for
zeolite; 97.84 ± 0.24 mg/g for Fe3O4@Z). The results clearly
showed that no significant matrix effect was observed in the
effective removal of RR120 from wastewater; zeolite and
Fe3O4@Z could be used to purify dye-containing wastewater
with high adsorption performance.
3.8. Comparison of Fe3O4@Z with other adsorbents
The type of adsorbent has a significant impact on adsorp-
tion. The adsorbent’s adsorption capacity was often
increased after chemical and/or heat treatment, however in
some cases, the opposite was seen. In recent years, many
adsorbents have been used for RR120 removal. The dye
adsorption conditions and adsorption capacities of the
adsorbents developed in these studies were investigated. In
the study by Dehghani et al. optimum conditions for RR120
removal on chitosan/zeolite composite were investigated,
and the RR120 removal percentage was found to be 91.2
under optimum conditions. The study reported the adsorp-
tion capacity as 19.60 mg/g.[13] To remove RR120 from an
aqueous solution, tunable Schiff’s base-cross-linked chitosan-
glutaraldehyde (CS-GLA) was developed and applied.
Different ratios of TiO2 nanoparticles were loaded into the
CS-GLA’s structure, and its adsorption capacity was found
to be 103 mg/g at 303 K.[75] Table S5 shows the adsorption
ability of several adsorbents toward RR120, as reported in
the literature. When compared to these adsorbents,
Fe3O4@Z has better adsorption performance and a greater
adsorption capacity. It is concluded that Fe3O4@Z has a lot
of potential to treat wastewater using RR120 dye.
4. Conclusion
Composites made of zeolites showed better benefits than
raw zeolites for the adsorption of several hazardous substan-
ces from water sources. Due to the ability to modify their
physical and chemical characteristics, such as pore size and
porosity of the adsorbent by varying the Si/Al ratio, nano-
composites are more suited for removing big molecules. In
this study, zeolite obtained from the K€utahya region, which
is abundant in our country, was used as an adsorbent to
remove Reactive Red 120 textile dye. In addition, it was
made composite with iron oxide nanoparticles, aiming to
increase the adsorption capacity. The adsorbents were char-
acterized by FTIR, SEM-EDX, XRF, XRD, BET methods,
and Fe3O4@Z composite adsorbent was successfully
obtained. The maximum adsorption amount for RR120
removal was reached at zeolite and Fe3O4@Z pH 1.50. It
was found that while the adsorption process accelerated
JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY 9
with the increase in temperature for both adsorbents, the
amount of adsorbed RR120 decreased with the increase in
temperature. Also, this was supported because the adsorp-
tion mechanisms proceeded with the pseudo-second-order
kinetic model and the k2 values increased with temperature.
It was observed that the adsorption of RR120 onto zeolite
and Fe3O4@Z followed the Langmuir and Freundlich iso-
therms, respectively, and the maximum adsorption capacity
was found to be decreased with increasing temperature. It
was also our conclusion that a multi-layered formation
occurred due to the placement of Fe3O4 nanoparticles on
the zeolite layers. Thus, RR120 adsorption, which takes place
only on the zeolite surface, takes place in the inner layers
and the surface due to the composite formation. Thus, an
increase in the adsorption capacity of the natural zeolite is
observed. Compositing zeolite and nanoparticles, which are
frequently used for adsorption, prevents the coagulation of
nanoparticles and increases the adsorption capacity of the
zeolite. Although the adsorption capacity obtained from this
study was lower than those treated with activated carbon
and its composites, it was satisfactory compared to zeolite
composites. However, the use of Fe3O4@Z adsorbent for
removing reactive dyes is interesting because of its low cost
and easy removal from the aqueous solution. From the
obtained thermodynamic data, it was determined that the
dyestuff adsorption process took place spontaneously
(DGo<0), exothermic (DHo<0), and regular (DSo<0), in
addition; the negative value of entropy change suggests
decreased randomness during adsorption. It shows that the
adsorption of RR120 on zeolite and Fe3O4@Z is not affected
by organic and inorganic pollutants in synthetic wastewater
and Fe3O4@Z composite adsorbent is a promising alterna-
tive for RR120 adsorption. On the other hand, the indus-
trial-scale applicability of the synthesized adsorbent for
environmental cleaning and recovery studies is needed.
ORCID
Çigdem Ay http://orcid.org/0000-0002-8283-0678
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