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OPEN Lead ferrite‑activated

carbon magnetic composite
for efficient removal of phenol
from aqueous solutions: synthesis,
characterization, and adsorption
studies
Esmaeil Allahkarami1, Abolfazl Dehghan Monfared1*, Luis Felipe Oliveira Silva2 &
Guilherme Luiz Dotto3

A novel lead ferrite-magnetic activated carbon (lead ferrite-MAC) composite was developed using the
chemical co-precipitation method. Instrumental analyses such as X-ray diffraction (XRD), scanning
electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and Brunauer–Emmett–
Teller (BET) analysis were performed to characterize adsorbent. The uptake of phenol from aqueous
solutions using the developed adsorbent was compared to that of pristine activated carbon. The
maximum adsorption capacity of lead ferrite-MAC composite (145.708 mg/g) was more than that of
pristine activated carbon (116.606 mg/g) due to the metal hydroxides coated on activated carbon
since they improve the retention of phenol on the available active sites of adsorbent and create
an additional electrostatic interaction with the phenol adsorbate. Regarding the high value of the
coefficient of determination (R2) and adjusted determination coefficient (R2adj), coupled with the lower
values of average relative error (ARE) and minimum squared error (MSE), it can be found that the
isothermal data for the lead ferrite-MAC adsorbent were in agreement with the isotherm models of
Redlich-Peterson and Langmuir. From the kinetic viewpoint, pseudo-second-order and linear driving
force models explained the phenol adsorption data for both adsorbents. The reusability tests for
lead ferrite-MAC composite revealed that after six cycles, 85% of the initial adsorption capacity was
maintained. The developed adsorbent can be successfully applied to uptake phenol from aqueous
solutions.

Phenols are the most common contaminants generated by petrochemical units, coal gasification sites, and oil
­refineries1, 2. They are mainly applied to produce phenolic resins, adhesives and epoxy resins, and polyamide for
different ­uses3. However, phenolic compounds are extremely t­ oxic4, lead to unpleasant odor and taste of drinking
water, and endanger living o ­ rganisms5, 6. Therefore, they should be removed from the aqueous solution. Dif-
ferent approaches are used for removing phenolic compounds from waste streams, including activated s­ ludge7,
­bioremediation8, membrane ­filtration9, solvent ­extraction10, and ­adsorption11. Table 1 shows the advantages/
disadvantages of mentioned techniques. Adsorption is the most efficient method for wastewater decontamina-
tion applications due to its efficiency, selectivity, low operating cost, and high adsorption capacity. Also, it does
not produce toxic ­substances12, 13.
There are different adsorbents such as m ­ inerals14, biological m
­ aterials15, polymer m
­ aterials16, and activated
­carbon17 to uptake phenol from different aqueous solutions. Koduru et al.18 examined the uptake of bisphenol
A (BPA) from water using goethite/activated carbon composite in a batch system. According to their report, the

1
Department of Petroleum Engineering, Faculty of Petroleum, Gas and Petrochemical Engineering, Persian Gulf
University, Bushehr 75169‑13817, Iran. 2Department of Civil and Environmental, Universidad de La Costa, CUC​,
Calle 58 # 55‑66, Barranquilla, Atlántico, Colombia. 3Chemical Engineering Department, Federal University of
Santa Maria, UFSM, Roraima Avenue 1000, Santa Maria, RS 97105900, Brazil. *email: [email protected]

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Method Advantages Disadvantages References

Relatively low cost Inefficient for treating high phenol concentration 30
Activated sludge
Straightforward process The complexity of adsorbent regeneration
Straightforward process Inefficient for treating high molecular weight polycyclic aromatic 8, 31
Bioremediation
Good selectivity hydrocarbons
Good selectivity and efficiency Need for high solvent concentrations 32, 33
Solvent extraction
Good process kinetics Relatively high cost
Process complexity
Small space requirements, 9, 34
Membrane filtration Relatively high cost
Efficient process
Pre-conditioning
Simple process
Slow process
Efficient process 35
Adsorption pH dependence
Selective process
Non-destructive operation
Relatively low cost

Table 1.  Advantages/disadvantages of methods used for the removal of phenol.

kinetic and equilibrium data were in agreement with the pseudo-second-order model and Freundlich isotherm,
respectively. Park et al.19 powdered activated carbons impregnated with iron oxide nanoparticles and used it to
uptake bisphenol A and natural organic matter from the aqueous solution. They found that the pH of the solu-
tion had no significant effect on BPA removal, but acidic conditions gave a slightly reduced sorption capacity,
possibly because of weaker hydrogen bonding between iron oxide and ­BPA20. Lingamdinne et al.21 synthesized
magnetic inverse spinel iron oxide nanoparticles using a biogenic methodology and used it for the removal of
pollutants from the aqueous solutions. The batch adsorption studies concluded that the adsorption of Pb(II) and
Cr(III) was the monolayer adsorptions on the homogenous surface of the developed adsorbent. In addition, the
kinetic data were in agreement with the pseudo-second-order kinetic model.
Promisingly, the application of activated carbon for wastewater decontamination purposes is of great interest
in recent years. In this way, the fabrication and improvement of the sorbent properties is the topic of research.
Din et al.22 fabricated a type of activated carbon from coconut shell (MNAC) and studied its application for the
uptake of phenol. The rate-limiting step of phenol adsorption onto MNAC was a chemical reaction because their
kinetic data were consistent with the pseudo-second-order model. According to the Langmuir isotherm, the
maximum adsorption capacity for this adsorbent was found to be 205.8 mg/g. Iron oxide/carbon nanocomposites
are frequently used as effective adsorbent materials to uptake different pollutants from the aqueous ­solutions23.
Ianoş et al.24 investigated the adsorption of the dyes Acid Blue 129, Methylene Blue, Rhodamine 6G, and Acid
Orange 7 on iron oxide/carbon nanocomposites. However, the development of metal ferrite coated carbon
composites has gained great interest as adsorbents to remove c­ ontaminants25, 26. In general, ferrite materials
are of significant interest due to their high adsorption capacity, non-toxicity, and easy ­availability25. Regarding
the favorable capacity of such adsorbents, it is important to develop an activated carbon-based composite and
evaluate its possible application for wastewater treatment purposes. Spinel metal ferrites ­(MFe2O4, M = Zn, Mn,
Co, Pb, Ba, Sr, and so on) have face-centered cubic structures and ­M2+ and F ­ e3+ cations fill the coordination
places in tetrahedral and octahedral. The arrangement of spinel ferrites influences their structural, chemical, and
magnetic properties. On the other hand, the use of lead (Pb), barium (Ba), and strontium (Sr) in the composi-
tion of ferrite materials could improve the magnetic properties of the material. Magnetically modified carbon
materials have received great attention for wastewater treatment purposes. Many reports are available regard-
ing the preparation of magnetic carbon material, and these materials were applied for the removal of different
pollutions from the aqueous medium. These reported magnetically modified carbon materials have agreeable
advantages of easy recovery and high adsorption efficiency. Yang et al.27 prepared magnetic F ­ e3O4/AC for the
uptake of methylene blue from aqueous solutions. The application of ­MnFe2O4 and ­CuFe2O4 composites for the
uptake of contaminants were reported by Zhang et al.28. ­Feng29 prepared N ­ iFe2O4/AC composite for the uptake
of methylene blue, rhodamine B, and malachite green. There is no systematic research on the synthesize and
application of lead ferrite-activated carbon composite for the removal of pollutants from waste streams. Thus,
the main aim of this research is to develop a new adsorbent namely lead ferrite-activated carbon composite for
the uptake of phenol from waste streams.
In this research, a novel lead ferrite-activated carbon composite (lead ferrite-MAC) was prepared using
chemical co-precipitation. The phenol uptake using the developed adsorbent was compared to that of pristine
AC. The most influential factors like phenol concentration, contact time, and solution acidity on the performance
of phenol adsorption onto both adsorbents were separately investigated. In addition, X-ray diffraction (XRD),
scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller
(BET) analyses, and zeta potential measurement have confirmed physicochemical properties of the prepared
adsorbent. Furthermore, the data were evaluated using different equilibrium and kinetic models to comprehend
the mechanism of phenol adsorption onto both adsorbents. Finally, lead ferrite-MAC regeneration experiments
were carried out to assess the prepared adsorbent from the practical aspect.

Experimental procedure
Materials and reagents. 1000 mg/L stock phenol solution was prepared using a specific amount of phenol
(Merck, Darmstadt, Germany) in double-distilled water and mixed on a magnetic stirrer at 300 rpm. Then, it
was diluted to prepare the desired concentration of phenol solution. Activated carbon (P60, Hanil, Korea) was

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used with no further purification. All other chemical reagents [HCl, NaOH, ­FeCl3, ­PbCl2, and oleic acid (Sigma–
Aldrich)] were analytical grade.

Lead ferrite‑MAC preparation. 0.4 mol/L (25 mL) of F­ e3+ solution and 0.2 mol/L (25 mL) of P
­ b2+ solution
were mixed in double-distilled water under magnetic stirring. 2.5 g of powdered activated carbon (PAC) was
dispersed in 25 mL DD water under vigorous stirring. Then, the solution containing F ­ e3+ and ­Pb2+ was poured
into 25 mL of the PAC ­solution26. After that, a solution of NaOH (25 mL) was added to the system with continu-
ous magnetic stirring for 6 h until reaching the pH > 12. 3–4 drops (for 100 mL solution) of oleic acid were added
with continuous magnetic ­stirring36. The obtained precipitate was then washed with DD water and ethanol to
eliminate impurities. Finally, the obtained composite was separated and oven-dried at 60 °C. Finally, to complete
the crystallization of the metals, the developed material was pyrolyzed in a muffle furnace at 700 °C for 1 h with
a heating rate of 10 °C/min under an argon atmosphere. The formed material of lead ferrite-MAC was evaluated
for phenol adsorption from the aqueous solutions.

Lead ferrite‑MAC characterization. The XRD pattern was determined using an X-ray diffractometer
1140 using Cu Kα radiation. The surface chemical characterizations of the prepared adsorbent were scanned
from 400 to 4000 ­cm−1 using FTIR spectroscopy (Shimadzu IR instrument). The samples were analyzed mor-
phologically by scanning electron micrographs (SEM, Seron Technology, AIS2100). The ­N2 adsorption–desorp-
tion isotherms (Belsorp mini II model) were applied to obtain the specific surface area and pore size of the devel-
oped adsorbent. Magnetic characterization of the developed adsorbent was carried out by the vibrating-sample
magnetometer (VSM) at ambient temperature. In addition, zeta potential measurements at an initial phenol
concentration of 100 mg/L were carried out to determine the point of zero charges (­ pHpzc) (Zetasizer Nano ZS,
Malvern Instruments Inc., UK). The Smoluchowski equation (Eq. 1) calculated the zeta potential (ξ):
ξ εV
µ= (1)
4πηd
where µ is the electrophoretic mobility; ε and d are the dielectric constant of medium and the electrode separa-
tion, respectively; η and V are the viscosity of the suspension and the applied voltage, ­respectively37, 38.

Batch adsorption experiment. All adsorption tests were carried out in a glass vessel sealed with a rubber
cover at ambient temperature. The vessels were compressed with an aluminum cover to avoid the phenol losses
by ­volatilization39. Few drops of dilute NaOH and HCl solutions were applied to regulate the solution acidity.
After equilibrium, the mixture was filtered, and the phenol concentrations in the aqueous solutions were meas-
ured using spectrophotometry at 271 nm. The tests were repeated three times, and their mean values were con-
sidered as outputs. All other experimental conditions are depicted in the figure or table captions. The adsorbed
quantity of phenol (qe) was calculated as follows (Eq. 2):
(C0 − Ce )V
qe = (2)
m
C0 and Ce represent the equilibrium and initial phenol concentrations in solutions (mg/L), m indicates the
adsorbent quantity (g), and V denotes the aqueous phase volume (L).
Adsorption isotherm experiments for phenol adsorption were conducted in a beaker containing various initial
nitrate concentrations with the adsorbent dosage of 1.5 g/L at ambient temperature and pH 7.0. In this research,
the adsorption of phenol onto the adsorbents was evaluated by Dubinin–Radushkevich, Redlich-Peterson, Tem-
kin, Freundlich, and Langmuir models. The coefficient of determination ­(R2)40, 41, mean square error (MSE)42, and
average relative error (ARE)43 were applied as statistical criteria to evaluate the best fit to the experimental data.
Desorption experiments were carried out to evaluate the reusability of the developed adsorbent. In this
context, 0.15 g of the adsorbent was added to 100 mL of phenol solution (500 mg/L) at ambient temperature
(25 °C) and stirred for 4 h. Then, the adsorbent was separated from the solution and treated with 1 mol/L NaOH
solution. Afterward, the used adsorbent was dried in an oven at 100 °C for 30 min. The adsorption–desorption
cycles were repeated 6 times by using a similar adsorbent and initial phenol concentration.

Results and discussion

Lead ferrite‑MAC features. The XRD pattern of the adsorbent (lead ferrite-MAC) is shown in Fig. 1.
The prominent peaks representing 23.71°, 36.22°, 52.33°, 62.25°, 65.34°, 75.27°, and 85.51° were assigned to the
planes of (111), (220), (222), (400), (422), (440), and (620), respectively. These peak positions are related to the
presence of the spinel of the cubic structure. The spectra are in close agreement with JCPDS card No.04-0705 and
with the findings of previous ­reports44, 45.
Infrared spectroscopy provides information on the functional groups at the adsorbent surface. In this context,
FTIR spectra of adsorbent before and after phenol adsorption were performed (Fig. 2). Two bands at 1601.65 ­cm−1
and 3402.32 ­cm−1 were related to the bending vibration of H–O and absorbed water on the sample surface,
respectively. The bands that appeared at about 1110–1180 ­cm−1 were related to C–O and C–O–C bonds’ vibration
for activated ­carbon46, 47. The weak absorption band at 2920 ­cm−1 is shown, allotted to the symmetrical and asym-
metrical stretching vibration of the C­ H2 group. In addition, the bands at 2840–2940 ­cm−1 were related to the C–H
stretch. Two bands at 643 and 687 c­ m−1 are related to asymmetric bending vibration of Pb–O-Pb and Fe metal
oxide (M–O) bond, r­ espectively48. These findings confirmed the presence of Pb and Fe on the adsorbent surface.

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220
222

Intensity (a.u.)
111 400

422 620
440

20 30 40 50 60 70 80 90
2 Theta (degree)

Figure 1.  XRD pattern of lead ferrite-MAC.

(a)
Transmittance (%)

(b)

3900 3400 2900 2400 1900 1400 900 400

Wavenumber (cm-1)

Figure 2.  FTIR spectra of lead ferrite-MAC (a) after and (b) before phenol adsorption.

Some changes were observed in the spectrum of lead ferrite-MAC adsorbent after phenol adsorption (Fig. 2b).
The vibration mode for Pb–O–Pb and Fe–O–Fe shifted from 643 and 687 to 584 and 588 ­cm−1. The new band
at 1384 ­cm−1 indicated the phenolic structure presence. Moreover, the band appearing at about 3110–2938 ­cm−1
was related to the phenolic type C–H. A mono-substituted aromatic structure appears at 807 and 774 ­cm−1 in
the fingerprint region after phenol adsorption.
To study the morphology of lead ferrite-MAC composite and pristine activated carbon, scanning electron
microscopy analysis was applied. Figure 3a,c show the SEM photographs of the lead ferrite-MAC composite at
different magnifications. Furthermore, by comparing Fig. 3a,b, it can be seen that the lead ferrite-MAC composite
has more spherical particles than pristine activated carbon. In fact, pristine activated carbon has sharp-edged
particles. It can be seen that the precipitates of lead and iron were aggregated together on the surface of AC. X-ray
mapping in the SEM analyses can be used to identify the elemental distribution on the sample’s surface. As shown
in Fig. 3d,e, only elements Pb and Fe were found. It can be found that they were homogeneously distributed in
the lead ferrite-MAC composite.
Figure 4 demonstrates the N ­ 2 adsorption and desorption isotherm for both adsorbents. Based on the IUPAC
classification, both adsorbents have the pores of Type IV with an H3 hysteresis loop, representing that the adsor-
bents have a mesoporous structure with some microporous. The hysteresis loop at high relative pressure signifies
the possible mesopores’ nature. Furthermore, a small number of micropores within the developed adsorbent (lead
ferrite-MAC) was seen at a pressure of around 0 to around 0.2. The pore size distribution plot of the adsorbent
is shown in Fig. 4b. This curve indicates that the pores of the lead ferrite-MAC sample are generally distributed
within multi-scales. For lead ferrite-MAC composite, two peaks at 14 and 25 nm and the peak ranging from 1 to
2 nm imply mesopore and micropore regions, respectively. Also, it can be found that pristine activated carbon
and lead ferrite-MAC composite have a specific surface areas of 1023.9 and 774.53 ­m2/g and pore sizes of 4.013
and 11.89 nm, respectively. The total pore volume of lead ferrite-MAC adsorbent decreased a little, which may
attribute to the blockage of these pores by metal ferrites after precipitation of lead and iron on the surface of
activated carbon. However, the pore size of both adsorbents is very bigger than the phenol molecular size enabling
its transference inside the adsorbent.
The relative magnetization curve of lead ferrite-MAC was presented in Fig. 5. This curve was used to inves-
tigate the magnetic feature of the adsorbent. As a result, it was verified that the saturation magnetization of the
developed adsorbent was found to be 37.9 emu/g. Furthermore, it was found that the permanent magnet could
separate the developed adsorbent from the aqueous solutions. The saturation magnetization of lead ferrite-MAC

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Figure 3.  (a) and (c) SEM images of lead ferrite-MAC adsorbent at different scales, (b) SEM image of pristine
activated carbon (d) X-ray mapping of Pb, (e) X-ray mapping of Fe in the lead ferrite-MAC composite.

900 0.24
(a) (b)

Pristine activated carbon

600 Pristine activated carbon 0.16
Va (cm3(STP)/g)

Lead Ferrite-MAC
dVp/drp

300 0.08

Lead Ferrite-MAC

0 0
0 0.2 0.4 0.6 0.8 1 1 10 100
p/p0 rp (nm)

Figure 4.  (a) ­N2 adsorption/desorption isotherm and (b) BJH pore size distributions of lead ferrite-MAC.

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50

40

30

20

Magnetization (emu/g)
10

0
-30000 -20000 -10000 0 10000 20000 30000
-10

-20

-30

-40

-50

Magnetic field (Oe)

Figure 5.  Hysteresis curve of lead ferrite-MAC.

20

15
Pristine activated carbon
10 Lead Ferrite-MAC
Zeta potential (mV)

0
0 2 4 6 8 10 12 14
-5

-10

-15

-20

-25
pH

Figure 6.  Zeta potential of lead ferrite-MAC and pristine AC versus pH value.

composite is the range of saturation magnetization reported for other metal f­ errites27, 29. The magnetic metal fer-
rites when compared with the magnetic iron oxide particles have several important advantages. These materials
may have a narrow size distribution, whereas direct production of iron oxide nanoparticles leads to a widespread
size range. In addition, they exhibit a higher specific loss power than the iron oxide nanoparticles, which makes
them interesting as potential candidates for wastewater treatment purposes.
Figure 6 shows the zeta potential and p­ HPZC on the surface of lead ferrite-MAC and pristine AC. The values of
zero point charge for lead ferrite-MAC and pristine activated carbon were about 6.7 and 7.1, respectively. Thus,
the surface of the adsorbent presents negative sites to adsorb cations when p ­ HPZC < pH, whereas in the case of
pH < ­pHPZC the positive sites are presented to adsorb ­anions49, 50.
Given the toxicity of Pb and Fe elements, it is necessary to evaluate the leaching of Pb and Fe into water.
According to Environmental Protection Agency (EPA), the permissible levels of lead and iron in drinking water
are 0.05 and 0.1 mg/L, respectively. In this regard, a series of experiments were carried out in a glass vessel
sealed with a rubber cover at ambient temperature. The adsorbent and water (without phenol) were mixed with
constant stirring using a magnetic stirrer at a fixed value of pH (2–14) for 24 h. Then, the concentrations of Pb
and Fe were measured with an Agilant ICP-AES spectrometer. It can be found that at different values of pH, the
concentration of Pb and Fe are well below the permissible limit based on EPA. So, this high stable adsorbent can
be successfully used for wastewater treatment purposes.

Effect of pH on the phenol adsorption. Solution acidity is the most important variable influencing the
process. Indeed, solution acidity affects the surface charge of the sorbent surface and the state of phenol that
existed in the solution. The adsorption capacity of phenol onto lead ferrite-MAC and pristine AC was investi-
gated at an initial pH range of 2.0–12.0 (Fig. 7). The extent of phenol adsorbed onto lead ferrite-MAC increased
from 36.23 to 62.56 mg/g by increasing the pH of the solution from 2.0 to 7.0, respectively. In addition, the
amount of adsorption capacity for pristine AC increased from 23.45 to 43.41 mg/g by increasing the pH of the
solution from 2.0 to 7.0, respectively. When the solution pH decreases from about 7.0 to 2.0, the ­H+ concentra-
tion increases. The presence of more H ­ + in the solution makes the condition unfavorable for adsorption of phe-
nol, as emerges a competition between ­H+ and phenol for occupying the adsorption sites. Albeit, further increase

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70

60

Phenol adsorbed (mg/g)

50

40

30

20
Pristine activated carbon
10
Lead Ferrite-MAC

0
0 2 4 6 8 10 12 14
pH

Figure 7.  Influence of solution acidity on the phenol adsorption onto lead ferrite-MAC and pristine AC (25 °C,
adsorbent dosage = 1.5 g/L).

140

120
Phenol adsorbed (mg/g)

100

80

60
Pristine activated carbon
40
Lead Ferrite-MAC
20

0
0 100 200 300 400 500 600
Initial phenol concentration (mg/l)

Figure 8.  Influence of concentration on the phenol adsorbed onto lead ferrite-MAC and pristine AC (pH 7,
adsorbent dosage = 1.5 g/L, 25 °C).

in pH, beyond the value of 7.0, decreased the adsorption capacity of both adsorbents. As mentioned, the zero-
point charge values of lead ferrite-MAC and pristine AC were about 6.7 and 7.1, respectively, above which the
adsorbent surface presents negative charges. Besides, at the higher values of pH, the presence of higher ­OH− in
the solution cause the dissociation of ­H+ from the phenol, leaving them in the anionic dominant form. Therefore,
a repulsive electrostatic interaction prevailed that resulted in a reduction in the capacity of adsorption. Thus,
there would be an optimum pH condition (about 7 for the current study) around which the maximum uptake
is usually expected.

Equilibrium studies. The relationship between the quantity of phenol adsorbed onto lead ferrite-MAC and
pristine AC, and the phenol concentration in the equilibrium state at a fixed temperature presents an adsorption
isotherm. Adsorption isotherm provides essential information about the capability of the adsorption process
for wastewater decontamination ­applications13. According to Fig. 8, the extent of phenol absorbed onto both
adsorbents enhances by increasing the concentration of phenol until it reaches a plateau area, representing the
maximum adsorption capacity of lead ferrite-MAC and pristine AC. This shape is a favorable type of isotherm
and indicates that lead ferrite-MAC and pristine AC are good adsorbents for phenol.
There are different isotherm models in the literature to represent the equilibrium curves and extract informa-
tion about the s­ ystem13, 51. In this research, Freundlich, Langmuir, Redlich-Peterson, and Tempkin isotherms
were applied to explain the equilibrium adsorption (Fig. 9). The Langmuir isotherm assumes that all adsorption
sites have the same sorption activation energy and have no transmigration in the plane of the ­surface52. The Fre-
undlich isotherm was derived from the assumption that adsorption occurs on a heterogeneous surface through
a multilayer adsorption m ­ echanism53. The Tempkin isotherm considers the adsorbate–adsorbent i­ nteractions54.
These interactions decrease the heat of molecular adsorption in the layer. The distribution of binding energies
determines the adsorption ­process54. Redlich-Peterson55 behaves like the Freundlich isotherm at high con-
centrations of sorbate, and at a low concentration, it approximates Henry’s law. Their nonlinear equations are
presented as follows:

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Figure 9.  Isotherm curve of phenol adsorption by (a) lead ferrite-MAC and (b) pristine AC (pH 7, adsorbent
dosage = 1.5 g/L, 25 °C).

qm KL Ce
qe = (3)
1 + KL Ce

qe = KF Ce1/n (4)

qe = B ln(KT Ce ) (5)

KRP Ce
qe = β (6)
1 + aRP Ce
where qm is the theoretical saturation capacity (mg/g); KL is the Langmuir constant (L/mg); KF is the constant
of the Freundlich model indicating the adsorbent’s adsorption capacity (mg/g)(mg/L)−1/n; 1/n is the Freundlich
exponent; B (defined as RT/bT) (mg/g) is the Tempkin constant corresponding to the adsorption heat; KT is a
constant related to maximum binding energy (L/mg); T is temperature; R denotes the universal gas constant;
KRP (L/g), aRP (L/mg)β), and β are constants in Redlich-Peterson isotherm.
Table 2 shows the equilibrium parameters for the systems of phenol/lead ferrite-MAC and phenol/pristine
AC, according to Eqs. (3–6).
The parameter estimations were performed using proper script programming on Matlab 2017. Regarding the
higher values of coefficient of determination (R2) and adjusted determination coefficient (R2adj), coupled with the
lower values of average relative error (ARE) and minimum squared error (MSE) (Table 2), it can be found that the
isothermal data for Pristine AC were in agreement with the isotherm models of Tempkin and Redlich-Peterson.
As the number of surface groups and the phenol uptake are high for activated carbon, adsorbate–adsorbate
interactions are of major importance, justifying the relevant application of the Tempkin equation. In addition,
the isothermal data for lead ferrite-MAC were in agreement with the isotherm models of Redlich-Peterson and
Langmuir. These results indicate that the phenol molecules are adsorbed by specific sites of the lead ferrite-MAC
adsorbent, undergoing adsorption in a monolayer form. It has been found that the presence of metal hydroxides
on the surface of AC increases the adsorption capacity of phenol on lead ferrite-MAC (Table 2). This can be
explained in terms of the molecular coordination between phenol and metal ­hydroxides18 along with the active
sites of AC. The Freundlich constants and 1/n values also confirmed that the present adsorption results for phenol
on both adsorbents stemmed from physical and chemical interactions between the adsorbent and adsorbate.
According to isotherm parameters, the maximum adsorption capacity of the lead ferrite-MAC composite was
higher than that of pristine AC, which was in agreement with adsorption experimental trends. This difference
is due to the difference in the structure of the adsorbent because the composite of lead ferrite-MAC contains
additional metal hydroxides.
The Dubinin–Radushkevich (D–R) model also performed the analysis of the equilibrium data. This analysis
was realized to determine whether the adsorption process is chemical or ­physical56. This model assumes that
ionic species binding follows by multilayer adsorption. D–R equation is as follows:

ln(qe ) = ln(qs ) − KDR ε2 (7)

 
1
ε = RTln 1 + (8)
Ce
Being qs is the isotherm saturation capacity, and KDR is the D–R constant. The mean free energy is defined
as follows:

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Parameter
Model Lead ferrite-MAC Pristine AC
Langmuir
qm (mg/g) 145.708 116.606
KL (L/mg) 0.013 0.006
R2 0.9986 0.9984
R2adj 0.9982 0.9979
ARE (%) 1.872 1.429
MSE (mg/g)2 0.941 0.529
Freundlich
KF ((mg/g)(mg/L)−1/nF) 12.713 4.688
1/n (dimensionless) 0.392 0.486
R2 0.97863 0.9811
R2adj 0.97151 0.9782
ARE (%) 7.228 5.269
MSE (mg/g)2 14.778 6.995
Redlich-Peterson
KRP (L/g) 2.155 0.882
aRP (L/mg)nRP 0.024 0.019
nRP (dimensionless) 0.920 0.852
R2 0.9997 0.9998
R2adj 0.9995 0.9995
ARE (%) 0.724 0.423
MSE (mg/g)2 0.178 0.078
Tempkin
KT (L/mg) 76.173 92.349
bT (J/mol) 0.120 0.055
R2 0.9990 0.9969
R2adj 0.9987 0.9959
ARE (%) 1.086 1.893
MSE (mg/g)2 0.672 1.019

Table 2.  Isotherm parameters for phenol adsorption by lead ferrite-MAC and pristine AC.

1
E= √ (9)
−2KDR
The plot of [lnqe] vs. [ln2(1 + 1/Ce)] for the phenol adsorption onto lead ferrite-MAC and pristine AC presented
coefficients of determination of 0.9917 and 0.9979, respectively. The E value for both adsorbents was relatively
4 kJ/mol. According to the D–R model, chemical adsorption is favored at mean free energy (E) between 8 and
16 kJ/mol, while for E < 8 kJ/mol, adsorption proceeds physically. Therefore, the adsorption of phenol onto both
adsorbents may be conducted by a physical mechanism.

Adsorption kinetics. To identify the necessary time for equilibrium, the phenol uptake onto lead ferrite-
MAC and pristine AC at different initial phenol concentrations was examined versus contact time. The amount
of phenol absorbed on both adsorbents was measured at 0, 30, 60, 90, 120, 150, 180, 240, 360, and 480 min.
Figure 10 shows the phenol adsorption profiles onto lead ferrite-MAC and pristine AC at various initial phenol
concentrations. The adsorption of phenol at the initial time increased drastically and reached approximately a
constant value after 200 min. Therefore, the contact time of 180 min is enough to attain equilibrium. However, a
contact time of 300 min was selected to ensure completed equilibrium.
The reaction models of pseudo-first-order (PFO) (Eq. 10), pseudo-second-order (PSO) (Eq. 11), and Elovich
(Eq. 12)55, 57 were applied to comprehend better the adsorption mechanism according to the kinetic curves. All
these models consider adsorption as a reaction. It is noted that this fact is not true, but sometimes, these models
can complement the information about the adsorption process.
qt = q1 (1 − exp( − k1 t)) (10)

t
qt = 
(11)
  
1
k2 q22
+ qt
2

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Figure 10.  Kinetic curves of phenol adsorption by (a) lead ferrite-MAC and (b) pristine AC (pH 7, adsorbent
dosage = 1.5 g/L, 25 °C).

1
qt = ln(1 + abt) (12)
a
where k1 (1/min) and k2 (g/mg min) are the kinetics constants of PFO and PSO, respectively; q1 and q2 are the
theoretical values for the adsorption capacity (mg/g); b is the initial velocity (mg/g min); a is the desorption
constant of Elovich model (g/mg).
In addition to the reaction models, the linear driving force model (LDF)58, which is based on the mass transfer
phenomena, was applied in this research. LDF model is given by:
−
dq  −

= kLDF q∗ − q (13)
dt
−
q (t=0) = 0 (14)
−
where q is the average phenol adsorption capacity (mg/g), q∗ is the phenol adsorption capacity related to the
concentration in the liquid phase at equilibrium (mg/g−1), and kLDF is the LDF mass transfer coefficient (1/
min). In the case of this work, the Langmuir model presented the best fit for the equilibrium, so q* in Eq. (14)
was substituted by Eq. (3). In addition, the global mass balance of phenol in the batch (Eq. 2) was inserted in
Eq. (14), leading to:
 � −
� 
− K L C0 -(m/V )q
dq −
(15)

= kLDF  qm � −
� − q
dt 
1 + KL C0 -(m/V) q


The parameter kLDF can be related to the diffusivity inside the adsorbent (Dh) and the particle radius (R) ­by58:
R2 kLDF
Dh = (16)
15
The kinetic parameters of the systems phenol/lead ferrite-MAC and phenol/pristine AC, estimated by the
fitting of Eqs. (10), (11), (12), and (15) to the experimental data (Fig. 10), are depicted in Table 3. Among the
reaction models, the PSO model was the best to represent the data, with higher values of coefficient of determi-
nation (R2) and adjusted determination coefficient (R2adj), and lower values of average relative error (ARE) and
minimum squared error (MSE) (Tables 3, 4). The parameter q2 of such model for lead ferrite-MAC and pristine
AC increased from 47.397 and 35.177 mg/g to 121.963 and 82.395 mg/g, respectively when the initial phenol
concentration increased from 100 to 500 mg/L. However, the rate of this increase was successively lower. Both
facts are related to the progressive increase in the surface coverage.
In the same way, the parameter k2 for lead ferrite-MAC and pristine AC raised from 8.531 × ­10–4 and
4.365 × ­10–4 g/mg min to 6.706 × ­10–4 and 1.160 × ­10–3 g/mg min, respectively with the increase in initial phenol
concentration (Tables 3, 4). This behavior shows that the adsorption phenomenon was progressively faster when
the initial concentration increased. This fact is explained by the external and internal concentration gradients
that are higher at higher phenol concentrations.
The LDF mass transfer model could also explain the phenol adsorption on both adsorbents. In this sense, it
can be found that the phenol adsorption on lead ferrite-MAC and pristine activated carbon occurs according
to the diffusion in a homogeneous adsorbent from the mass transfer aspect. This mechanism was also assumed
by Franco et al.59, studying the phenol adsorption on activated carbon prepared from fruit wastes of the Ceiba
speciosa. The values of kLDF and Dh corroborated the same trend of k2. Besides, Dh for lead ferrite-MAC and

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Initial phenol concentration (mg/L)

Model 100 200 300 400 500
PFO
q1 (mg/g) 41.886 71.205 89.667 102.731 111.503
k1 (1/min) 0.0462 0.0433 0.0642 0.0769 0.0821
R2 0.9678 0.9465 0.9739 0.9771 0.9657
R2adj 0.9675 0.9460 0.9732 0.9768 0.9652
ARE (%) 5.426 6.986 4.455 6.697 4.020
MSE (mg/g)2 7.412 9.044 5.169 10.252 8.589
PSO
q2 (mg/g) 47.397 82.694 100.389 114.702 121.963
k2 (g/mg min) 8.531 × ­10–4 4.203 × ­10–4 5.860 × ­10–4 5.844 × ­10–4 6.706 × ­10–4
R2 0.9941 0.9944 0.9986 0.9974 0.9989
R2adj 0.9933 0.9937 0.9985 0.9970 0.9988
ARE (%) 2.600 2.556 1.170 1.598 0.975
MSE (mg/g)2 1.112 3.153 1.179 3.000 1.340
Elovich
a (g/mg) 0.151 0.080 0.089 0.086 0.093
b (mg/g min) 16.860 17.449 186.604 499.364 1988.181
R2 0.9672 0.9684 0.9827 0.9797 0.9866
R2adj 0.9631 0.9644 0.9805 0.9772 0.9849
ARE (%) 6.178 6.151 4.206 4.433 3.497
MSE (mg/g)2 6.145 17.805 14.860 22.968 17.327
LDF
kLDF (1/s) 2.93 × ­10–4 4.46 × ­10–4 7.37 × ­10–4 8.17 × ­10–4 9.02 × ­10–4
Dh ­(cm2/s) 4.41 × ­10–9 8.96 × ­10–9 1.83 × ­10–8 1.94 × ­10–8 2.06 × ­10–8
R2 0.9666 0.9588 0.9748 0.9841 0.9906
R2adj 0.9624 0.9535 0.9716 0.9821 0.9894
ARE (%) 5.43 6.06 5.01 4.02 3.05
MSE (mg/g)2 5.99 9.28 10.54 9.23 7.15

Table 3.  Kinetic parameters of phenol adsorption by lead ferrite-MAC.

pristine activated carbon ranged from 4.41 × ­10–9 and 1.41 × ­10–9 to 2.06 × ­10–8 and 8.43 × ­10–8 ­cm2/s, respectively.
These values are in the same range as those found by Franco et al.59 (activated carbon) and Ocampo-Pérez et al.60
(bituminous coal).

Proposed mechanism of phenol adsorption. According to isotherm parameters, the maximum

adsorption capacity of lead ferrite-MAC composite was more than that of pristine activated carbon, which was
in agreement with adsorption experimental trends. This difference is due to the metal hydroxides coated on acti-
vated carbon since they improve the retention of phenol on the available active sites of the adsorbent and create
an additional electrostatic interaction with the phenol adsorbate. Electrostatic attraction between metal hydrox-
ides and the acidic –OH of phenol can be one of the possible mechanisms of phenol adsorption onto lead ferrite-
MAC ­composite61. Some changes in the bending vibration of M–O before and after phenol adsorption (FTIR
analysis) confirmed the electrostatic interaction of phenol with lead ferrite-MAC. Another possible mechanism
of phenol adsorption onto the developed adsorbent is hydrogen-bonding interactions between the functional
groups of activated carbon (CO and OH) with phenolic –OH. In addition, π–π electron donor–acceptor interac-
tions between aromatic rings of phenol and the surface of the adsorbent affect the adsorption p ­ rocess62.

Comparison with other adsorbents and reusability of lead ferrite‑MAC. Selective phenol adsorp-
tion using different adsorbents like activated ­carbon22, biological ­materials31, and ­minerals14 has been investi-
gated. Table 5 indicates the comparison of phenol removal using different adsorbents. The adsorption capacity
of the lead ferrite-MAC adsorbent in this research is not maximum. However, it is better than some adsorbents
such as magnetic activated carbon cobalt nanoparticles; tithonia diversifolia activated carbon, biochar produced
from an oil palm frond, diethylenetriamine-modified activated carbon, activated carbon obtained from black
wattle bark waste, ­NiFe2O4-powdered activated carbon, and biochar made of the pine fruit shells (BC550).
Therefore, it can be concluded that the adsorbent prepared here is promising and competitive.
Another attribute of lead ferrite-MAC that makes it a promising material is reusability. The reusability of an
adsorbent is a crucial factor from the practical aspect, making it a commercially attractive and green method. Dif-
ferent methods include heating regeneration, solvent washing, and chemical and petrochemical regeneration for
regenerating ­adsorbents63, 64. Among them, solvent washing is a well-known method for recovering and reusing

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Initial phenol concentration (mg/L)

Model 100 200 300 400 500
PFO
q1 (mg/g) 16.229 22.228 60.125 67.749 73.952
k1 (1/min) 0.012 0.016 0.028 0.025 0.024
R2 0.9013 0.9001 0.9913 0.9777 0.9578
R2adj 0.9008 0.8989 0.9902 0.9768 0.9752
ARE (%) 8.738 9.616 3.902 5.494 4.900
MSE (mg/g)2 14.412 15.986 1.977 9.252 7.589
PSO
q2 (mg/g) 35.177 57.401 69.321 77.442 82.935
k2 (g/mg min) 4.365 × ­10–4 3.782 × ­10–4 5.396 × ­10–4 8.920 × ­10–4 1.160 × ­10–3
R2 0.9912 0.9877 0.9974 0.9997 0.9998
R2adj 0.9901 0.9862 0.9971 0.9996 0.9998
ARE (%) 4.316 4.641 1.647 0.490 0.391
MSE (mg/g)2 0.831 3.243 1.017 0.169 0.119
Elovich
a (g/mg) 0.151 0.080 0.089 0.086 0.093
b (mg/g min) 16.860 17.449 186.604 499.364 1988.181
R2 0.9672 0.9684 0.9827 0.9797 0.9866
R2adj 0.9631 0.9644 0.9805 0.9772 0.9849
ARE (%) 11.863 10.384 6.749 6.490 4.992
MSE (mg/g)2 6.145 17.805 14.860 22.968 17.327
LDF
kLDF (1/s) 1.97 × ­10–4 2.99 × ­10–4 3.81 × ­10–4 4.02 × ­10–4 4.62 × ­10–4
Dh ­(cm2/s) 1.41 × ­10–9 8.05 × ­10–9 2.25 × ­10–8 4.41 × ­10–8 8.43 × ­10–8
R2 0.9723 0.9634 0.9571 0.9769 0.9682
R2adj 0.9701 0.9612 0.9489 0.9747 0.9667
ARE (%) 4.213 6.108 10.183 5.550 5.812
MSE (mg/g)2 3.871 4.104 6.586 5.707 5.234

Table 4.  Kinetic parameters of phenol adsorption by pristine AC.

Adsorbent qm (mg/g) References

Activated carbon from fruit wastes of the Ceiba speciosa 156.7 59

67
Activated carbon/zirconium oxide composite 166.7
64
Magnetic activated carbon cobalt nanoparticles 107.50
68
Tithonia diversifolia activated carbon 50.55
69
Biochar produced from an oil palm frond 62.89
70
Diethylenetriamine-modified activated carbon 18.12
71
Activated carbon obtained from black wattle bark waste 98.57
72
NiFe2O4-powdered activated carbon 93.25
73
Biochar obtained from the pine fruit shells (BC550) 26.74
Pristine activated carbon 116.61 Present study
Lead ferrite-magnetic activated carbon 145.71 Present study

Table 5.  Comparison of phenol adsorption using diverse adsorbents.

the adsorbent. So, the solvent washing method was applied to regenerate the developed adsorbent. The regenera-
tion experiments of lead ferrite-MAC were conducted for six cycles using 1 mol/L NaOH. When washing with
NaOH, sodium phenolate is formed because of the reaction of sodium hydroxide with phenol. This product can
be easily desorbed and dissolved in the solution of ­solvent65, 66. The obtained results are presented in Fig. 11. The
adsorption capacity of phenol onto the adsorbent decreased with the number of cycles. This phenomenon have
resulted from the saturation of active sites on the surface of the adsorbent, the protonation of available functional
groups on the surface of the adsorbent, and/or the destruction of adsorbent particles during successive cycles of
adsorption/desorption. However, the adsorbent maintained 85% of this maximum potential after these cycles.

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Adsorption Desorption

120

100

Phenol adsorbed (mg/g)

80

60

40

20

0
Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6

Figure 11.  Phenol adsorbed onto lead ferrite-MAC in successive cycles (C0 = 500 mg/L, 4 h, 25 °C, pH 7,
adsorbent dosage = 1.5 g/L).

Cf (μg/L) Removal efficiency (%)

Parameters Ci (μg/L) AC Lead ferrite-MAC AC Lead ferrite-MAC
Phenol 98.83 19.32 4.12 80.45 95.83
Copper 23.76 6.12 3.23 74.24 86.41
Chromium 9.7 2.11 1.12 78.25 88.45
Nickel 12.67 4.03 1.27 68.19 89.98
Zinc 7.83 2.01 0.93 74.33 88.12
Cobalt 10.04 2.12 1.22 78.88 87.85
Manganese 7.32 1.98 Not detected 72.95 100.00
Arsenic 5.1 0.92 Not detected 81.96 100.00

Table 6.  Competitive phenol adsorption from the real industrial wastewater using lead ferrite-MAC and
pristine AC.

It can be found that lead ferrite-MAC has interesting adsorption potential after six cycles of regeneration. The
results confirmed the practical usefulness of the lead ferrite-MAC composite.

Phenol removal from the real industrial wastewater

To evaluate the practical application of the lead ferrite-MAC adsorbent for the removal of phenol from the real
industrial wastewater, 0.15 g of the lead ferrite-MAC composite and pristine activated carbon was stirred with
100 ml of wastewater sample taken from the nearby industrial area of Parsian, Bandarabbas, Iran. To remove solid
particles and impurities, the wastewater sample was filtered. The wastewater sample was analyzed for the contents
of pollutants. The major pollutants of this sample were phenol, copper, chromium, nickel, zinc, cobalt, manga-
nese, and arsenic as presented in Table 6. It is noted that the original sample spiked with 90 μg/L of phenol. The
experiment was carried out at an ambient temperature, stirring speed of 300 rpm, and a stirring time of 400 min.
The developed adsorbent (lead ferrite-MAC) showed significant adsorption efficiency for several pollutants.
Results indicated that the lead ferrite-MAC composite could efficiently remove phenol from waste streams and
the removal was relatively 96%. Furthermore, the developed adsorbent removed other pollutants like copper,
chromium, nickel, zinc, cobalt, manganese, and arsenic with efficiencies of relatively 90%. Therefore, the devel-
oped adsorbent can be successfully applied with high efficiency for the practical removal of phenol from waste
streams to produce healthy water using a stable and efficient adsorbent.

Conclusions
In this research, a novel lead ferrite-activated carbon composite (lead ferrite-MAC) was developed and compared
with pristine AC for the uptake of phenol, where the most influential operating parameters were analyzed. Instru-
mental analyses such as XRD, SEM, FTIR, zeta potential, and BET analysis were carried out to characterize lead
ferrite-MAC adsorbent. lead ferrite-MAC was preponderantly a mesoporous adsorbent, with some microporous,
and presented a surface area of 747.53 m ­ 2/g and pore size of 11.89 nm. The zeta potential was 6.7, and a saturation
magnetization of 37.9 emu/g proved the magnetic character. Concerning the phenol adsorption potential for both
adsorbents, the best pH was 7.0. Results indicated that the maximum adsorption capacities for lead ferrite-MAC
composite and pristine activated carbon were 145.708 and 116.606 mg/g, respectively. Regarding the high value of
the coefficient of determination (R2) and adjusted determination coefficient (R2adj), coupled with the lower values
of average relative error (ARE) and minimum squared error (MSE), it can be found that the isothermal data for
lead ferrite-MAC adsorbent were in agreement with the isotherm models of Redlich-Peterson and Langmuir.
According to isotherm parameters, the maximum adsorption capacity of lead ferrite-MAC composite was more

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than that of pristine activated carbon, which was in agreement with adsorption experimental trends. This differ-
ence is due to the metal hydroxides coated on activated carbon since they improve the retention of phenol on the
available active sites of the adsorbent and create an additional electrostatic interaction with the phenol adsorbate.
The mean free energy for the systems of phenol/lead ferrite-MAC and phenol/pristine AC was relatively 4 kJ/
mol, indicating a physical mechanism. Among the kinetic models, the PSO model was the best to represent the
data, with higher values of coefficient of determination ­(R2) and adjusted determination coefficient (­ R2adj), and
lower values of average relative error (ARE) and minimum squared error (MSE). The phenol adsorption onto
lead ferrite-MAC and pristine AC was relatively fast and explained by the diffusion in a homogeneous solid. The
diffusion coefficient values, Dh, for lead ferrite-MAC and pristine AC ranged from 4.41 × ­10–9 and 1.41 × ­10–9 to
2.06 × ­10–8 and 8.43 × ­10–8 ­cm2/s, respectively. In addition, the adsorption capacity of lead ferrite-MAC is within
the literature range, but the material can be reused 6 times. The results presented in this work point out that lead
ferrite-MAC is a promising and competitive adsorbent to uptake phenol from aqueous media.

Data availability
The datasets used and/or analyzed during the current study available from the corresponding author on reason-
able request.

Received: 1 May 2022; Accepted: 17 June 2022

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Author contributions
E.A.: conceptualization, methodology, software, investigation, data curation, writing- original draft preparation.
A.D.M.: conceptualization, methodology, data curation, investigation, supervision, visualization, investigation,
writing- reviewing and editing. L.F.O.S.: software, validation, writing- reviewing and editing. G.L.D.: writing-
reviewing and editing, visualization, software, validation.

Competing interests
The authors declare no competing interests.

Additional information
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