molecules

Article
Adsorption of Crystal Violet Dye Using Activated Carbon of
Lemon Wood and Activated Carbon/Fe3O4 Magnetic
Nanocomposite from Aqueous Solutions: A Kinetic,
Equilibrium and Thermodynamic Study
Rauf Foroutan 1 , Seyed Jamaleddin Peighambardoust 1 , Seyed Hadi Peighambardoust 2 , Mirian Pateiro 3 and
Jose M. Lorenzo 3,4, *

1 Faculty of Chemical and Petroleum Engineering, University of Tabriz, Tabriz 5166616471, Iran;
[email protected] (R.F.); [email protected] (S.J.P.)
2 Department of Food Science, College of Agriculture, University of Tabriz, Tabriz 5166616471, Iran;
[email protected]
3 Centro Tecnológico de la Carne de Galicia, Rúa Galicia No. 4, Parque Tecnológico de Galicia,
32900 San Cibrao das Viñas, Ourense, Spain; [email protected]
4 Área de Tecnología de los Alimentos, Facultad de Ciencias de Ourense, Universidad de Vigo,
32004 Vigo, Ourense, Spain
* Correspondence: [email protected]; Tel.: +34-988-548-277







Citation: Foroutan, R.; Abstract: Activated carbon prepared from lemon (Citrus limon) wood (ACL) and ACL/Fe3 O4 mag-
Peighambardoust, S.J.; netic nanocomposite were effectively used to remove the cationic dye of crystal violet (CV) from
Peighambardoust, S.H.; Pateiro, M.; aqueous solutions. The results showed that Fe3 O4 nanoparticles were successfully placed in the
Lorenzo, J.M. Adsorption of Crystal structure of ACL and the produced nanocomposites showed superior magnetic properties. It was
Violet Dye Using Activated Carbon of found that pH was the most effective parameter in the CV dye adsorption and pH of 9 gave the
Lemon Wood and Activated maximum adsorption efficiency of 93.5% and 98.3% for ACL and ACL/Fe3 O4 , respectively. The
Carbon/Fe3 O4 Magnetic Dubinin–Radushkevich (D-R) and Langmuir models were selected to investigate the CV dye adsorp-
Nanocomposite from Aqueous
tion equilibrium behavior for ACL and ACL/Fe3 O4 , respectively. A maximum adsorption capacity
Solutions: A Kinetic, Equilibrium and
of 23.6 and 35.3 mg/g was obtained for ACL and ACL/Fe3 O4 , respectively indicating superior
Thermodynamic Study. Molecules
adsorption capacity of Fe3 O4 nanoparticles. The kinetic data of the adsorption process followed
2021, 26, 2241. https://doi.org/
the pseudo-second order (PSO) kinetic model, indicating that chemical mechanisms may have an
10.3390/molecules26082241
effect on the CV dye adsorption. The negative values obtained for Gibb’s free energy parameter
Academic Editor: Lucian Baia (−20 < ∆G < 0 kJ/mol) showed that the adsorption process using both types of the adsorbents was
physical. Moreover, the CV dye adsorption enthalpy (∆H) values of −45.4 for ACL and −56.9 kJ/mol
Received: 23 March 2021 for ACL/Fe3 O4 were obtained indicating that the adsorption process was exothermic. Overall,
Accepted: 11 April 2021 ACL and ACL/Fe3 O4 magnetic nanocomposites provide a novel and effective type of adsorbents to
Published: 13 April 2021 remove CV dye from the aqueous solutions.

Publisher’s Note: MDPI stays neutral Keywords: activated carbon; magnetic nanoparticles; aqueous solution; cationic dye; isothermal
with regard to jurisdictional claims in models
published maps and institutional affil-
iations.

1. Introduction
Water is one of the most important and effective substances in human life and other
Copyright: © 2021 by the authors. living beings. It is used every day in various industries and is exposed to various chemicals
Licensee MDPI, Basel, Switzerland. and thus can be contaminated. In recent decades, water pollution has become a serious
This article is an open access article threat to the environmental system, therefore, reducing pollutants from industrial wastew-
distributed under the terms and ater before discharging to the environment is necessary [1]. The industrial wastewater
conditions of the Creative Commons
usually contains several organic and toxic substances that can be harmful to human and
Attribution (CC BY) license (https://
aquatic life [2]. Dyes are the first known contaminants in the industrial wastewater streams.
creativecommons.org/licenses/by/
Various industries such as food processing, paper, cosmetics, leather, textiles, printing and
4.0/).

Molecules 2021, 26, 2241. https://doi.org/10.3390/molecules26082241 https://www.mdpi.com/journal/molecules

Molecules 2021, 26, 2241 2 of 19

pharmaceuticals discharge large amounts of wastewater containing dyes polluted with

toxic compounds into the environment [3,4]. Annually, it is estimated that 50,000 tons of
organic dyes are disposed of worldwide [5].
Dyes used in industry are classified into three categories of cationic dyes (all base
dyes), anionic (direct, acidic and reactive dyes) and non-ionic (disperse dyes) [6,7]. Cationic
dyes, being as more dangerous than other types, are widely used in the industry. It is
reported that 12% of the annual production (about 700,000 tons) of cationic dyes is wasted
through industrial water streams polluting the environment [8,9]. Crystal violet (CV) dye is
a cationic dye of triphenyl methane with high intensity and it is used in various industries
such as pharmaceuticals, paper, textiles and printing inks [10]. CV dye is more toxic than
negative dye [11] and if present in water can reduce the penetration of sunlight and disrupt
the process of photosynthesis [12]. In addition, CV dye in certain concentrations can cause
various diseases and illnesses such as respiratory failure, eye irritation, increased heart rate,
skin irritation, blindness, cyanosis, cancer and mutagenesis [10]. Therefore, it is necessary
to remove the CV dye from industrial wastewater streams before entering the environment.
Numerous methods have been used to remove various dyes from aqueous solutions
and industrial wastewaters, among which nanofiltration, ozonation, flocculation, reverse
osmosis, adsorption, electrochemical and biological degradation, chemical oxidation, and
photocatalytic degradation are the most extensively used methods [13,14]. Despite to
establishing such methods, attempts to find suitable methods with high efficiency, low
cost and ease of process are scarce [11]. Adsorption is one of the methods received a lot
of attention due to its advantages such as being cheap, having process flexibility with no
sludge production, the process simplicity, efficiency and high speed [15,16]. Conventional
adsorbents such as activated carbon, biowaste and clay have been used to remove dyes
from water, but most of them have low adsorption capacity with low selectivity [17]. In
this regard, the use of nanoparticles (magnetic or non-magnetic) to produce adsorbents
with high active surface is a very effective method, because nanoparticles owing to their
porous structure and high surface area can improve the efficiency of the adsorption process
in removing dye substances [18]. The advantage of using magnetic nanoparticles over
non-magnetic ones in addition to improving the adsorbent efficiency, is that they can be
easily separated from aqueous solutions [19]. Fe3 O4 magnetic nanoparticles provide an
additional advantage of being economic with low toxicity can be used in the adsorption
process for the removal of various pollutants [20].
In the adsorption process, various adsorbents such as activated carbon, natural fibers,
carbon nanotubes, zeolites, polymeric materials [21] and magnetic nanocomposite [4,22]
have been used. However, there is a room for new challenges in the development of
novel materials as adsorbents in the water treatment process. In the present study, lemon
wood was used as a suitable primary source in the preparation of activated carbon and
activated carbon/Fe3 O4 magnetic nanocomposite and the ability and efficiency of these
nanocomposites in removing CV dye from aqueous solution were evaluated. In addition,
the effects of parameters such as temperature, contact time, adsorbent dose, initial CV dye
concentration and contact time on the CV dye adsorption process were investigated.

2. Results and Discussion

2.1. Characteristics of Nanocomposites
Fourier-transform infrared spectroscopy (FTIR) analysis for ACL and ACL/Fe3 O4
magnetic nanocomposite samples was performed before and after the CV dye adsorption
process and the results are shown in Figure 1a. In the structure of ACL and ACL/Fe3 O4
magnetic nanocomposite, high intensity vibrations have been observed in the range of
3418–3419 cm−1 , which is due to –OH tensile vibrations in the structure of the desired adsor-
bents. Also, vibrations have been observed in the range of 2852–2922 cm−1 which is caused
by C-H vibrations in the structure of the adsorbents. In the structure of ACL, wavenumbers
of 1640, 1584, 1432, 1167, 669–881, 608 and 450 cm−1 corresponded to vibrations of C=C or
C=N, C=O, C=C or CH, C-O-C or C=O, C-H, and C-C bonds, respectively [23,24].
Molecules 2021, 26, 2241 3 of 19

Figure 1. (a) Fourier-transform infrared spectroscopy (FTIR) analysis for ACL and ACL/Fe3 O4 magnetic nanocomposites
before and after CV dye adsorption process; and (b) Vibrating sample magnetometer (VSM) analysis for Fe3 O4 and
ACL/Fe3 O4 magnetic nanocomposites.

After placing Fe3 O4 nanoparticles in the ACL structure, the range of peaks in the ACL
structure was changed, which could be due to the interaction of Fe3 O4 with functional
groups in the ACL structure. It should also be noted that in the ACL/Fe3 O4 magnetic
nanocomposite structure, a high intensity peak in the range of 567 cm−1 has been observed
due to Fe-O vibrations [25], and shows that Fe3 O4 magnetic nanoparticles have been
successfully incorporated into the ACL structure. After the CV dye adsorption process
using ACL and ACL/Fe3 O4 magnetic nanocomposite, the range and intensity of peaks in
the adsorbent structure was changed, which could be due to the interaction and placement
of the CV dye with the adsorbent surface. For example, after the adsorption process, the
range of -OH vibrations in the ACL structure and the ACL/Fe3 O4 magnetic nanocomposite
changed from 3418 cm−1 and 3419 cm−1 to 3431 cm−1 and 3430 cm−1 , respectively, which
indicates that hydrogen bonds have been formed in the adsorption process. In addition,
the results of FTIR analysis showed that functional groups such as -OH, C=O, C=C and
C-O-C were effective in the CV dye adsorption process.
Magnetic property is one of the important features of magnetic adsorbents in the
adsorption process, because it facilitates the separation of the adsorbent from the aqueous
solution and reduces the process cost. Therefore, the magnetic properties of Fe3 O4 nanopar-
ticles and ACL/Fe3 O4 magnetic nanocomposite were studied in the range of −8000 Oe
to 8000 Oe and the results are shown in Figure 1b. According to the results, the magnetic
saturation values for Fe3 O4 nanoparticles and ACL/Fe3 O4 magnetic nanocomposite were
84.3 and 32.0 emu/g, respectively.
Nitrogen physical adsorption experiments were studied to determine structural prop-
erties such as active surface area, pore volume and pore diameter for ACL and ACL/Fe3 O4
magnetic nanocomposites and the results are shown in Figure 2. The adsorption-desorption
isotherm of N2 for both samples followed a type IV isotherm with a residual ring at a
relative pressure of P/P0 in the range of 0.5–1, indicating the presence of mesoporous struc-
ture of the material [26] and the adsorption of the monolayer [27]. In addition, the pore
diameter size was in the range of 2–50 nm (according to the IUPAC standards) indicated
that ACL and ACL/Fe3 O4 magnetic nanocomposites have a mesoporous structure. Based
on the analysis, the amount of specific active surface for ACL samples and ACL/Fe3 O4
magnetic nanocomposites was 25.99 and 38.69 m2 /g, respectively. The increased active
level of ACL/Fe3 O4 nanocomposites was due to the presence of Fe3 O4 nanoparticles in the
structural layers of ACL. It is also noteworthy to mention that with the placement of Fe3 O4
nanoparticles, the pore volume in the ACL structure was also increased, which confirms
the placement of Fe3 O4 nanoparticles and the increase in the distance between the layers
and the ACL pores.
Molecules 2021, 26, 2241 4 of 19

Figure 2. Nitrogen adsorption-desorption analysis for ACL and ACL/Fe3 O4 magnetic nanocomposite samples.

The decrease in the amount of magnetic saturation in the desired magnetic nanocom-
posite can be due to the presence of a non-magnetic matrix (ACL) and the reduction of
magnetic particles in the structure of the desired nanocomposite [28]. It is noteworthy that
the absence of hysteresis ring showed that Fe3 O4 nanoparticles and ACL/Fe3 O4 magnetic
nanocomposite have superior magnetic properties, and can be easily separated from the
aqueous solution using an external magnetic field.
Scanning electron microscopy (SEM), Map and energy-dispersive X-ray spectroscopy
(EDX) was performed to investigate the surface changes in the ACL and ACL/Fe3 O4
magnetic nanocomposite before and after the CV dye adsorption process. The results
Figure 3a show that ACL has a porous structure and the composition of elements C and
O in its structure is 84.4% and 15.6%, respectively. Also, the results of the Map analysis
showed that the elements are well distributed in the ACL structure Figure 3b. After ACL
modification using Fe3 O4 magnetic nanoparticles, particles of different sizes were observed
in the pores and layers of the ACL, which could represent the Fe3 O4 nanoparticles formed
in the ACL structure Figure 3d. Also, EDX and Map analysis confirmed the presence of
Fe ions (9.92%) in the ACL structure, which indicates that Fe3 O4 nanoparticles have been
successfully placed in the ACL structure and have a good interaction Figure 3e,f. After CV
dye adsorption process using ACL and ACL/Fe3 O4 magnetic nanocomposite, significant
changes in the structure and pores on the adsorbent surface were observed Figure 3g,h. The
changes may be due to the presence of CV dye in the adsorbent layers and pores, which
confirms that ACL and ACL/Fe3 O4 magnetic nanocomposite have the ability to remove
CV dye from aqueous solution.

2.2. The Effect of pH

Based on previous studies, it has been reported that the initial pH is one of the
effective parameters in the efficiency and adsorption capacity, because it can affect the
surface loads and the degree of ionization of functional groups in the adsorbent surface [29].
For this purpose, the effect of pH on surface loads and adsorption efficiency of CV dye was
investigated using both adsorbents in the initial pH range 2 to 10 Figure 4a,b.
Molecules 2021, 26, 2241 5 of 19

Figure 3. SEM, Map and EDX analyzes for: (a–c) ACL; (d–f) ACL/Fe3 O4 magnetic nanocomposite; (g) ACL after CV dye
adsorption, and (h) ACL/Fe3 O4 magnetic nanocomposite after CV dye adsorption.

According to the results, the pHzpc values for Fe3 O4 , ACL and ACL/Fe3 O4 magnetic
nanocomposite were determined to be 7.4, 7.1 and 6.48, respectively. At pH > pHzpc and pH
< pHzpc , the adsorbent has negative and positive surface charges, respectively. According
to the obtained results, by increasing the pH from 2 to 10, the CV dye adsorption efficiency
using both adsorbents has increased and significant dye removal has been performed in
alkaline media (pH > pHzpc ). This condition can be due to the strong gravitational force
and the reduction of repulsive force between the adsorbent surface and the CV dye [30]. It
should be noted that the low efficiency of CV in acidic environments using both adsorbents
can be due to the presence of H+ ions in aqueous solution, which competes with CV color
to be located on active adsorbent sites [30,31].
The mechanism of CV dye adsorption using ACL/Fe3 O4 magnetic nanocomposite in
pH > pHzpc and pH < pHzpc values is shown in Figure 4c. The mechanism of the CV dye
adsorption process in the acidic and alkaline pH ranges is shown in Figure 4c.
Molecules 2021, 26, 2241 6 of 19

Figure 4. (a) The effect of pH on the surface loads of adsorbents; (b) The effect of pH on the efficiency of the adsorption
process (temperature 25 ◦ C, contact time 60 min, adsorbent dose 1.25 g/L, CV dye concentration 10 mg/L), and (c) the
mechanism of the CV dye adsorption process in the acidic and alkaline pH ranges.

2.3. Contact Time and Kinetic Study

One of the important and effective factors in the adsorption process is the duration time
of interaction between the adsorbent surface and the contaminant, which has an effective
role in the kinetics and speed of the adsorption process. The effect of contact time on CV
dye adsorption efficiency using ACL adsorbents and ACL/Fe3 O4 magnetic nanocomposite
were investigated in the time range of 5–140 min and the results are shown in Figure 5a.
According to the obtained results, the adsorption process using ACL and ACL/Fe3 O4
magnetic nanocomposite has been done in three stages. The first stage (5–20 min) is faster
than other stages, which can be due to the presence of empty and available active sites
for the CV dye. After 80 min, the rate of adsorption process decreased significantly and
the efficiency of adsorption process did not change significantly, which could indicate
the equilibrium adsorption of the desired process. Therefore, the equilibrium time for
the CV dye adsorption process was determined using ACL and ACL/Fe3 O4 magnetic
nanocomposite 80 min and 60 min, respectively. The kinetic behavior of the adsorption
process can be used to find useful and effective information about the adsorption process
and equilibrium time. For this purpose, to investigate the kinetic behavior of the adsorption
process in the time range of 5–140 min, Pseudo-first order (PFO), Pseudo-second order
Molecules 2021, 26, 2241 7 of 19

(PSO), Elovich and intraparticle diffusion kinetic model (Weber-Morris) were used and
their nonlinear equations are arranged as follows:
 
Pseudo − first order (PFO) : qt = qe 1 − e−k1 t (1)

k2 q2e t
Pseudo − second order (PSO) : qt = (2)
1 + k2 qe t
1
Elovich : qt = ln(αβ t) (3)
β
√
Intraparticle diffusion : qt = Kint t+I (4)
where, qt and qe are the amount of CV dye adsorption capacity per gram of dry adsorbent
at any time and equilibrium time (mg/g), respectively; k1 is adsorption rate constant
(min−1 ); k2 is adsorption rate constant of PSO kinetic model (g/mg/min); α is the initial
adsorbance (mg/g/min); β is the desorption constant (g/mg); the Kint constant is the intra
particle diffusion rate (mg/g min0.5 ); and the value of I is the kinetic constant of the intra
particle diffusion kinetic model that gives ideas about the boundary layer thickness.

Figure 5. (a) contact time effect (pH = 9, temperature 25 ◦ C, adsorbent dose 1.25 g/L, initial CV concentration 10 mg/L),
Nonlinear relationship of PFO, PSO and intraparticle diffusion kinetic models for (b) ACL, and (c) ACL/Fe3 O4 magnetic
nanocomposite, and (d) linear relationship of Weber-Morris model for ACL and ACL/Fe3 O4 magnetic nanocomposite.

The linear and nonlinear relationship of kinetic models for the CV adsorption process
using ACL and ACL/Fe3 O4 magnetic nanocomposite were shown in Figure 5b,c and the
kinetic variables specified are listed in Table 1. The results of the kinetic behavior study
showed that the PSO model has a greater ability to describe the kinetic behavior of the
Molecules 2021, 26, 2241 8 of 19

process than other kinetic models, because it has a higher correlation coefficient (R2 ) and
higher adsorption capacity (qe.cal ), and the root-mean-square error (RMSE) is less. In
addition, the α parameter for the CV dye adsorption process using the ACL/Fe3 O4 mag-
netic nanocomposite is higher than that of ACL, which shows that ACL/Fe3 O4 magnetic
nanocomposite has a greater tendency to interaction CV dye and is also consistent with
experimental results.

Table 1. Kinetics constants and parameters determined using kinetic models for the adsorption
process.

Adsorbent
Kinetic Model
ACL ACL/Fe3 O4
Pseudo-first order
qe cal 7.51 7.808
KP1st 0.0608 0.0819
R2 0.9151 0.9484
RMSE 0.5142 0.3687
Pseudo-second order
qe.cal 8.545 8.648
KP2st 0.009 0.0138
R2 0.9664 0.9730
RMSE 0.3235 0.2666
Elovich equation
α (mg/g min) 2.049 4.34
β (g/mg) 0.6328 0.7057
R2 0.9642 0.9156
RMSE 0.3337 0.4719
Intraparticle diffusion
Ki,1 (mg/g min1/2 ) 1.0021 1.0836
I1 (mg/g) 0.7179 1.0916
R2 0.9887 0.9965
Ki,2 (mg/g min1/2 ) 0.8855 0.7777
I2 (mg/g) 0.6332 2.4091
R2 0.9807 0.954
Ki,3 (mg/g min1/2 ) 0.0247 0.0081
I3 (mg/g) 7.4444 7.8024
R2 0.9495 0.9696

In addition, the correlation coefficient (R2 ) values determined using the Alovitch
model for ACL and ACL/Fe3 O4 magnetic nanocomposite was 0.9642 and 0.9156, respec-
tively, which indicates that chemical mechanisms and ion exchange are also effective in
the adsorption process [32], and by modifying ACL using Fe3 O4 nanoparticles the effect of
chemical mechanism and ion exchange is reduced. In the adsorption process, PFO and PSO
models are not able to investigate and determine the mechanism of the adsorption process.
There are several stages involved in the adsorption process, and one of the important steps
that can control the speed of the adsorption process is film diffusion and intraparticle
diffusion [33].
For this purpose, the intraparticle diffusion model is used to explain the different
stages of the adsorption process. The line diagram of the intra-particle diffusion model for
the CV dye adsorption process using the adsorbents used in Figure 5d is shown. When the
line passes through the origin, it can be suggested that intraparticle diffusion is the only
mechanism controlling the adsorption process. The linear relationship of the Weber-Morris
model shows that the adsorption process has three stages that are consistent with the
experimental results. Also, the results showed that intraparticle diffusion is not the only
mechanism controlling the adsorption process and the boundary layer is a mechanism
control in a multi-stage system [34]. The first stage (2.236 ≤ t0.5 ≤ 5.22) is related to the film
Molecules 2021, 26, 2241 9 of 19

diffusion mechanism that the contaminant immediately enters the adsorbent surface [35].
The second (5.186 ≤ t0.5 ≤ 7.824) and the third stage (7.824 ≤ t0.5 ≤ 7.9908) represent
intraparticle diffusion and equilibrium condition, respectively [36].

2.4. Effect of Initial CV Content and Isotherm Study

The initial concentration of the dye can have a significant effect on the efficiency and
adsorption capacity of the process due to providing the necessary driving force for mass
transfer between the aqueous phase (aqueous solution containing dye) and the solid phase
(adsorbent). Figure 6a,b shows the effect of the initial concentration of CV dye in the range
of 10–80 mg/L on the efficiency and adsorption capacity. The results showed that with
increasing the initial concentration of CV dye, the efficiency of adsorption process using
for ACL and ACL/Fe3 O4 magnetic nanocomposite decreased from 95.78% and 98.34%
to 36.38% and 55.34%, respectively. The high removal efficiency at low concentrations of
dye solution can be due to the greater interaction of dye molecules with the surface and
active sites in the adsorbent structure. In addition, the decrease in adsorption efficiency at
high concentrations of CV dye could be due to the saturation of adsorbent active sites at
high concentrations of CV, limited active adsorbent sites or increased repulsive electrostatic
force between the adsorbent surface and CV dye in aqueous solution [37]. Although with
increasing the initial concentration of CV dye, the efficiency of the adsorption process
has decreased, but the adsorption capacity of adsorbents has increased. Increasing the
adsorption capacity of adsorbents by increasing the initial concentration of CV dye solution
can be due to the increased slope of the driving force of mass transfer from aqueous solution
to the surface of adsorbents, which has increased the penetration of dye molecules in the
internal pores and active sites in the structure of adsorbents [38]. Different isotherm models
can be used to investigate the equilibrium behavior between the desired pollutant and the
adsorbents used, as well as to determine the type of process.
In this study, the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D-R)
isotherm models were used to investigate the equilibrium behavior of the CV adsorption
process using ACL and ACL/Fe3 O4 magnetic nanocomposite. The Langmuir isotherm
model is based on the assumption that monolayer adsorption occurs at homogeneous active
sites in the adsorbent structure; while the Freundlich model is based on the assumption that
adsorption occurs at heterogeneous and non-uniform surfaces. The D-R model assumes
that the adsorbent surface used is heterogeneous and is used to show the chemical and
physical adsorption mechanism of the process [39]. The nonlinear equations of the isotherm
models used in this study are as follows:

qm kl Ce 1
Langmuir : qe = , RL = (5)
1 + kl Ce 1 + KL + C o
1
Freundlich : qe = kf Cen (6)
1
D − R : qe = qm exp( − βε2 ), ε = RTln(1 + ) (7)
Ce
RT
Temkin : qe = Bln(A × Ce ), B = (8)
bT
where, qe is the equilibrium adsorption capacity (mg/g); qm is the maximum adsorption ca-
pacity of the monolayer (mg/g); kL is the Langmuir adsorption constant, which represents
the binding energy (L/mg); kF and n are Freundlich model constants; bT (kJ/mol) and AT
(l/g) are Obedience model constants, R is universal constant of gases, T (K) is absolute
temperature, ε is polanyi coefficient, β is activity coefficient (mol2 /J2 ), which represents
the free energy of adsorption.
Molecules 2021, 26, 2241 10 of 19

Figure 6. (a,b) Effect of initial CV concentration on efficiency and adsorption capacity (pH = 9, contact time for ACL and
ACL/Fe3 O4 magnetic nanocomposite 80 and 60 min, temperature 25 ◦ C, adsorbent dose 1.25 g/L), Nonlinear relationship
of isotherm models for CV dye adsorption process using (c) ACL and (d) ACL/Fe3 O4 magnetic nanocomposite. Data are
mean of triplicate measurements. (a,b) the error bars indicate SD values.

The nonlinear relationship of the isotherm models used, the constants and the deter-
mined variables are shown in Figure 6c,d and Table 2, respectively.
As the results show, in the CV dye adsorption process using ACL and ACL/Fe3 O4
magnetic nanocomposite, D–R and Langmuir isotherm models have more ability to de-
scribe equilibrium data, respectively, which show that heterogeneous and homogeneous
surfaces are effective in the adsorption process, respectively. The values of n and RL pa-
rameters determined using the Freundlich and Langmuir isotherm models showed that
the adsorption process using both types of adsorbents used is desirable and physical. The
Kf parameter for the CV adsorption process was determined using ACL and ACL/Fe3 O4
magnetic nanocomposite to be 13.78 mg/g (L/mg)1/n and 18.25 mg/g (L/mg)1/n , respec-
tively, which shows that the bond between the cationic dye of CV and the surface of
the ACL/Fe3 O4 magnetic nanocomposite is greater and stronger compared to ACL [40].
Also, the average energy value (E) was determined using ACL and ACL/Fe3 O4 magnetic
nanocomposite 1.972 kJ/mol and 2.364 kJ/mol, respectively, which shows that the adsorp-
tion process is physical (E < 8 kJ/mol) [29,41,42] and is well consistent with the results of
the ∆G parameter. The determined parameters (bT and A) using Temkin model showed
that the interactions between the adsorbent surface and the desired cationic dyes are weak
and may be a physical adsorption process.
Molecules 2021, 26, 2241 11 of 19

Table 2. Constant isotherms and parameters determined for the CV dye adsorption process.

Adsorbent
Models
Parameters ACL ACL/Fe3 O4
qm (mg/g) 23.64 35.31
KL (L/mg) 1.469 1.366
Langmuir RL 0.008–0.063 0.009–0.68
R2 0.9704 0.9826
RMSE 1.122 1.435
n 6.5 4.595
Freundlich Kf (mg/g (L/mg)1/n ) 13.78 18.25
R2 0.78 0.891
RMSE 3.06 3.591
E (kJ/mol) 1.972 2.364
Dubinin–Radushkevich qm (mg/g) 22.53 31.91
(D–R) β (mol2 /J2 ) 1.285 × 10−7 8.969 × 10−8
R2 0.9838 0.8828
RMSE 0.8293 3.723
bT (kJ/mol) 0.837 0.45
Temkin AT (L/g) 94.77 30.79
R2 0.8415 0.9737
RMSE 2.597 1.904

2.5. Effect of Absorbent Dose

Absorbent dose is another effective parameter in the adsorption process that can
affect the efficiency and adsorption capacity of the adsorbent. The effect of adsorbent
dose on CV dye efficiency and adsorption capacity was investigated using ACL and
ACL/Fe3 O4 magnetic nanocomposite in the range of 0.5–5 g/L and the results are shown
in Figure 7. The results showed that with increasing the adsorbent dose of ACL and
ACL/Fe3 O4 magnetic nanocomposite from 0.5 g/L to 5 g/L, the adsorption efficiency
increased from 57.82% and 63.41% to 98.61% and 99.34%, respectively. Increasing the
adsorption efficiency by increasing the adsorbent dose can be due to increasing the number
of unsaturated and available active sites [43,44]. According to Figure 7a, the optimal
adsorbent dose for ACL and ACL/Fe3 O4 magnetic nanocomposite was determined to be
2 g/L and 1.25 g/L, respectively. After the optimal dose of adsorbent, the efficiency of the
adsorption process did not change significantly, which can be caused by various factors
such as decreasing the concentration of CV dye in aqueous solution and non-contact of
dye with active adsorbent sites, adsorbent particles collide with each other and reduce
the active surface [43]. In addition, according to the results Figure 7b, it can be mentioned
that with increasing the adsorbent dose, the adsorption capacity of adsorbents used in the
CV dye adsorption process has decreased, which can be due to the vacancy of active sites
of adsorbents in high doses, because the concentration of pollutants is constant, but the
number of active sites has increased and not all active sites of adsorbents have been used
well [45].
Molecules 2021, 26, 2241 12 of 19

Figure 7. Effect of adsorbent dose on (a) adsorption efficiency, and (b) adsorption capacity (pH = 9, temperature 25 ◦ C,
initial CV dye concentration 10 mg /L, contact time for ACL and ACL/Fe3 O4 magnetic nanocomposite 80 and 60 min,
respectively). Data are mean of triplicate measurements and error bars indicate SD values.

2.6. Effect of Temperature and Thermodynamic Study

Temperature is one of the important and effective parameters in the adsorption process
and it has been shown that this parameter affects the transfer process and the adsorption
kinetics of dyes. The effect of temperature on CV dye adsorption efficiency was inves-
tigated using ACL and ACL/Fe3 O4 magnetic nanocomposite in the range of 25–50 ◦ C
Figure 8a. The results showed that with increasing the temperature from 25 ◦ C to 50 ◦ C, the
efficiency of CV dye adsorption process using ACL and ACL/Fe3 O4 magnetic nanocom-
posite decreased from 97.43% and 98.34% to 90.73% and 92.48%, respectively. This indicates
the exothermic nature of the CV dye adsorption process using the adsorbents. Decreas-
ing the efficiency of the adsorption process with increasing temperature can be due to
the weakening of the physical bonds between the dye molecule and the active sites of
the adsorbent, increase the solubility of CV dye in aqueous solution, which makes the
interactions between the dye molecule and the solvent stronger than the adsorbent [46].
Therefore, a temperature of 25 ◦ C was determined as the optimal temperature for the CV
dye adsorption process using ACL and ACL/Fe3 O4 magnetic nanocomposite. Van’t Hoff
equation was used to investigate the behavior and determine thermodynamic parameters
such as enthalpy (∆H), entropy (∆S) and Gibbs free energy (∆G) in the temperature range
of 25–50 ◦ C Figure 8b and the results are shown in Table 3.
According to the results, the value of ∆G for the CV dye adsorption process using
ACL and ACL/Fe3 O4 magnetic nanocomposite has a negative value, which shows that
the adsorption process is spontaneous and possible [47]. Also, the value of the parameter
∆G for the adsorption process is in the range of kJ/mol −20 < ∆G < 0, which shows that
the adsorption process using both types of adsorbents is physical [48]. Also, the value of
∆H parameter for CV dye adsorption process was determined using ACL and ACL/Fe3 O4
magnetic nanocomposite −45.382 kJ/mol and −56.901 kJ/mol, respectively, which indi-
cates that the adsorption process is exothermic. Also, the value of the ∆S parameter was
negatively determined for the adsorption process, which indicates that random collisions
and irregularities at the adsorbent surface are reduced during the adsorption process.
According to the results, it seems that the parameter ∆H has a greater effect than the ∆S in
determining the negative value of ∆G [49].
Molecules 2021, 26, 2241 13 of 19

Figure 8. (a) The effect of temperature on the adsorption efficiency (pH = 9, contact time for ACL and ACL/Fe3 O4 magnetic
nanocomposite 80 and 60 min, respectively, adsorbent dose for ACL and ACL/Fe3 O4 magnetic nanocomposite 2 and
1.25 g/L, respectively, initial dye concentration of 10 mg/L); (b) the linear relation of van’t Hoff equation to determine
thermodynamic parameters. Data are mean of triplicate measurements. (a) error bars indicate SD values.

Table 3. Thermodynamic parameters for the CV dye adsorption process.

Adsorbent T (◦ C) ∆G◦ (KJ/mol) ∆H◦ (KJ/mol) ∆S◦ (J/mol·K)

25 −9.011
30 −8.958
35 −8.551
ACL −45.382 −120.594
40 −8.071
45 −6.793
50 -6.128
25 −10.117
30 −10.241
35 −9.793
ACL/Fe3 O4 −56.901 −154.915
40 −8.666
45 −7.105
50 −6.742

2.7. Comparison of Adsorption Capacity

The adsorption capacity of different adsorbents used in the adsorption process, de-
pending on the primary source of the adsorbent, the process conditions of adsorption,
adsorption modification, and the type of contaminant can be different. Today, extensive
research has been done to find adsorbents with good adsorption capacity and low eco-
nomic cost. Due to the mentioned reasons, in the present study, the adsorption capacity
of ACL/Fe3 O4 and ACL magnetic nanocomposites was compared with other natural and
synthetic adsorbents used in the CV dye adsorption process and the results are reported
in Table 4. The results show that the ACL/Fe3 O4 and ACL magnetic nanocomposite has
a higher ability to absorb CV from aqueous solutions compared to many natural and
synthetic adsorbents and can be used as an effective adsorbent in the CV dye adsorption
process.
Molecules 2021, 26, 2241 14 of 19

Table 4. Comparison of ACL adsorption capacity and ACL/Fe3 O4 magnetic nanocomposite with
other adsorbents used in CV removal process.

Adsorbent qe (mg/g) CV Dye Reference

Magnetite alginate 37.5 [50]
P(AAm-MA)/MMT 20.36 [51]
Starch-g-poly (acrylic acid)/ZnSe 10 [52]
Poly (acrylamide)-kaolin composite
23.8 [2]
hydrogel
Polyvinyl alcohol/agar/maltodextrin 19.17 [53]
Guar gum/bentonite bionanocomposite 167.929 [54]
Soil-silver nanocomposite 1.918 [55]
Activated carbon 35.64 [56]
NaOH-modified rice husk 44.876 [57]
Leaf biomass of Calotropis procera 4.14 [58]
TLAC/Chitosan composite 0.269–2.375 [59]
Chitin nanowhiskers 59.52 [60]
AC-Fe2 O3 ·NPLs 16.5 [61]
Chitin-psyllium based aerogel 227.11 [62]
Poly(benzofuran-co-arylacetic acid)-FA 25.10 [63]
Azolla and fig leaves modified with
25 [64]
magnetite iron oxide nanoparticles
Solid waste of rosewater extraction 78.24 [65]
Eucalyptus camdulensis sawdust-derived
54.7 [66]
biochar (Ec-bio)
ACL 23.64 This study
ACL/Fe3 O4 magnetic nanocomposite 35.31 This study

3. Materials and Methods

3.1. Materials
Lemon wood was obtained from a local garden and used as a primary source in the
production of activated carbon. Sodium hydroxide (NaOH), hydrochloric acid (HCl), iron
(III) chloride hexahydrate (FeCl3 ·6H2 O), iron (II) tetrachloride (FeCl2 ·4H2 O), crystal violet
(CV) dye was prepared from Merck (Darmstadt, Germany). To prepare a standard CV dye
solution, a certain amount of dye was dissolved in deionized water. To prepare aqueous
solutions containing CV dye for adsorption test, stock solution was diluted with deionized
water and used. Deionized water was used for solutions in all stages of the experiments.

3.2. Synthesis of Adsorbents

The lemon wood was washed with tap water and dried at 105 ◦ C for 48 h. The dried
wood was burnt at 700 ◦ C for 3 h to prepare the desired carbon. The prepared carbon was
then pulverized using a kitchen mill and stored at room temperature. In order to produce
ACL/Fe3 O4 magnetic nanocomposite, co-precipitation method was used. For this purpose,
at first, 2 g of ACL was added to an aqueous solution (100 mL) containing Fe (III) and Fe (II)
ions in a 1:2 molar ratio and stirred for 40 min using a magnetic stirrer. At the end of this
time, NaOH solution with a concentration of 3 M (30 mL) was added dropwise and stirred
for 50 min at 80–90 ◦ C using a magnetic stirrer. The produced magnetic nanocomposite
was isolated using an external magnetic field and collected after washing for several times
followed by drying at 105 ◦ C for 24 h. The obtained powder of magnetic nanocompositewas
Molecules 2021, 26, 2241 15 of 19

stored at ambient temperature. Figure 9 shows an overview of the ACL/Fe3 O4 magnetic

nanocomposite synthesis process.

Figure 9. A schematic illustration of the productions process and structure of ACL/Fe3 O4 magnetic
nanocomposite.

3.3. Characteristics of Adsorbents

Fourier-transform infrared spectroscopy (FTIR) analysis using a Tensor 27, spectropho-
tometer (Bruker, Bremen, Germany) [67] was used to characterize the chemical structure of
ACL and ACL/Fe3 O4 magnetic nanocomposite in the range of 4000–400 cm−1 . Nitrogen
physical adsorption experiments (BET test) using Accelerated Surface Area and Porosity
(ASAP) measurement (model ASAP 2020, Micrometrics Instruments, Norcross, GA, USA)
was used to determine the structural properties of ACL samples and ACL/Fe3 O4 magnetic
nanocomposites such as active surface area, pore volume and pore diameter. The mor-
phology and porous structure of ACL and ACL/Fe3 O4 nanoparticles were investigated
using scanning electron microscopy (MIRA3, TESCAN, Brno, Czech Republic) with energy
dispersive X-ray spectroscopy (EDX). Vibrating sample magnetometer (VSM) analysis
(model 7400-S, Lake-Shore Cryotronics, Westerville, OH, USA) was performed to evaluate
the magnetic properties of Fe3 O4 and the ACL/Fe3 O4 magnetic nanocomposite in the
range of −8000 Oe to 8000 Oe.

3.4. Adsorption Study

CV dye adsorption was investigated using ACL adsorbents and ACL/Fe3 O4 magnetic
nanocomposite in 100 mL tubes and discontinuously. In the process of adsorption of
CV dye, the effect of various parameters such as pH (2–10), contact time (5–140 min),
temperature (25–50 ◦ C), adsorbent dose (0.5–5 g/L) and initial concentration of CV dye
(10–80 mg/L) were evaluated on the efficiency of the adsorption process. To investigate the
behavior of the adsorption process in the desired pH range, a certain amount of ACL and
ACL/Fe3 O4 magnetic nanocomposite was added to 50 mL of aqueous solution containing
CV dye at the desired pH and stirred for 60 min. At the end of the time, the adsorbents were
separated from the aqueous phase and the amount of CV dye remaining in the aqueous
medium was determined using a UV-vis spectrophotometer (model Cary 100, Agilent
Technologies, Santa Clara, CA, USA) at 592 nm and the maximum adsorption efficiency
was determined as the optimal value. After determining the optimal pH, other parameters
were examined at the optimal pH and in the desired ranges, and the maximum efficiency
Molecules 2021, 26, 2241 16 of 19

was determined. At each stage, the efficiency and adsorption capacity were determined
from Equations (9) and (10), respectively:

CVi − CVe
 
R(%) = × 100 (9)
CVi

V
qe = (CVi − CVe ) × (10)
m
where, CVi and CVe are the initial concentration and final concentration of CV dye (mg/L),
V is the volume of solution used (L) and m (g/L) is the amount of adsorbent used, and qe
(mg/L) is the adsorption capacity of the adsorbents.

4. Conclusions
In this study, activated carbon prepared from lemon wood (ACL) and magnetic
nanocomposite of ACL were used as an effective and low-cost adsorbent in the adsorption
process of cationic crystal violet (CV) dye from aqueous solution. The results of FTIR
analysis showed functional groups such as C=O, C-O, Fe-O and -OH in the structure of
ACL and ACL/Fe3 O4 magnetic nanocomposites, which can be effectively used in the
process of CV dye adsorption. VSM analysis also showed superior magnetic properties of
Fe3 O4 nanoparticles and ACL/Fe3 O4 magnetic nanocomposite that can be easily separated
from the aqueous solution using an external magnetic field. The results of different
equilibrium models showed that the CV dye adsorption equilibrium data using ACL and
ACL/Fe3 O4 magnetic nanocomposite followed the D-R and Langmuir models, respectively.
Based on isotherm studies, it was shown thatmonolayer and homogeneous surfaces are
more effective than heterogeneous surfaces. ACL/Fe3 O4 magnetic nanocomposite showed
significantly higher adsorption capacity than ACL nanoparticles. In addition, parameters
such as n, RL , E and bT showed that the adsorption process is desirable and physical
and the CV dye can be easily separated from the surface of the desired adsorbents. The
kinetic data of the adsorption process for both types of adsorbents followed the PSO kinetic
model, which shows that chemical reactions can also be effective in the adsorption process.
The study of thermodynamic parameters was in good agreement with the experimental
data and showed that the CV dye adsorption process is spontaneous, exothermic, and
during the adsorption process the amount of irregularity is reduced. Concluding, ACL
and ACL/Fe3 O4 magnetic nanocomposite can be introduced and used as an effective and
efficient adsorbent in removing CV dye from aqueous solution and industrial wastewaters.

Author Contributions: Conceptualization, R.F. and S.J.P.; writing—original draft preparation, R.F.,
S.H.P. and S.J.P.; writing—review and editing, R.F., S.H.P., S.J.P., M.P. and J.M.L. All authors have
read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding authors.
Acknowledgments: Authors would like to acknowledge Urmia University (Urmia, Iran) for sup-
porting this research.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Samples of the compounds ACL and ACL/Fe3 O4 are available from the
authors.
Molecules 2021, 26, 2241 17 of 19

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