Materials Chemistry and Physics 284 (2022) 126047

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Magnetite-induced topological transformation of 3D hierarchical MgAl

layered double hydroxides to highly dispersed 2D magnetic
hetero-nanosheets for effective removal of cadmium ions from
aqueous solutions
Daniel Gherca *, 1, Adrian Iulian Borhan , Marius Mugurel Mihai , Dumitru-Daniel Herea ,
George Stoian , Tiberiu Roman, Horia Chiriac , Nicoleta Lupu , Gabriela Buema **, 1
National Institute of Research and Development for Technical Physics, 47 Mangeron Boulevard, 700050, Iasi, Romania

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Magnetic 2D hetero-nanosheets of type

MgAl-LDH + Fe3O4 were successfully
fabricated.
• The platelet-like magnetic composite
had Fe3O4 nanoparticles dispersed on
lamella.
• Topological transformation of 3D Hier­
archical MgAl-LDH to the 2D LDH
nanosheets.
• MgAl-LDH + Fe3O4 was an effective
adsorption capacity for Cd(II) of 109.9
mg/g.
• The adsorption mechanisms for Cd(II)
was proposed.

A R T I C L E I N F O A B S T R A C T

Keywords: The study shows the synthesis of highly dispersed magnetic hetero-nanosheets through topological trans­
3D hierarchical MgAl LDH formation of 3D Hierarchical MgAl layered double hydroxides in the presence of Fe3O4 nanoparticles. The
Cadmium adsorption platelet-like hierarchical nano-heterostructures consisted of 10 nm Fe3O4 magnetic nanoparticles dispersed over
Co-precipitation
the surface of MgAl-LDH lamella. The as-prepared biphasic self-assembled nanocomposite was successfully used
Magnetic hetero-nanosheets
as an adsorbent for decontamination of spiked cadmium wastewater at room temperature. A comprehensive
Water remediation
physico-chemical characterization of structural and textural features, as well as the magnetic properties of the
prepared nanocomposites were carried out by using complementary techniques such as scanning electron mi­
croscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffractometer (XRD), vibrating sample
magnetometer (VSM), Dynamic light scattering (DLS) analysis, Brunauer-Emmett-Teller (BET) surface area and
Zeta potential respectively. Moreover, the influences of certain parameters including pH, adsorbent dosage,
initial cadmium concentration, and contact time were extensively studied in terms of profiling the adsorption
capacity of the hierarchical nano-heterostructures. Different adsorption isotherm (Langmuir, Freundlich, Tem­
kin, and Redlich-Peterson) in linear and nonlinear forms were applied. According to the results, Freundlich and

* Corresponding author.
** Corresponding author.
E-mail addresses: dgherca@phys-iasi.ro (D. Gherca), gbuema@phys-iasi.ro (G. Buema).
1
These authors contributed equally.

https://doi.org/10.1016/j.matchemphys.2022.126047
Received 10 January 2022; Received in revised form 11 March 2022; Accepted 22 March 2022
Available online 29 March 2022
0254-0584/© 2022 Elsevier B.V. All rights reserved.
D. Gherca et al. Materials Chemistry and Physics 284 (2022) 126047

Redlich-Peterson models fitted the data. On the other hand, three kinetic models were used, including pseudo-
first order, pseudo-second order (linear and nonlinear forms), and intraparticle diffusion.The results were
explained through a pseudo-second-order model, reaching the equilibrium in 60 min. The optimum recom­
mended pH and adsorbent dose are 5 and 1.4 g/L, respectively. Comprehensive characterization revealed that
the synthesized materials are suitable candidates as adsorbents in Cd (II) adsorption techniques with maximum
adsorption capacities of 80.6 mg/g, 91.7 mg/g, and 109.9 mg/g. Furthermore, the regeneration investigation
highlighted the adsorbents’ performance after three cycles of adsorption/desorption.

1. Introduction
Chemical pollutants, mainly heavy metals, released from the
wastewaters of different industries are listed as a critical threat to the
environment and human health [1–4]. The adsorption process for heavy
metals removal is an important environmental subject especially due to
the advantages of low cost, large quantities of available adsorbents, high
adsorption capacity, and easy regeneration potential [5–11]. Because
cadmium ion is one of the most hazardous heavy metals [12–14] and is
non-essential for human health, many research have focused on its
adsorption. Cadmium accumulates mostly in the kidneys and liver
whereas the related contamination is most commonly associated with
metal industry and sewers [15]. Even in low concentrations, the pres­
ence of cadmium in the human body through drinking water or other
sources, leads to major biological consequences, including erythrocyte
destruction, nausea, salivation, diarrhea, and muscle cramps, as well as
kidney damage, persistent lung issues, skeletal deformities [16] and
death [17].
The allowable limit of cadmium according to the World Health Or­
ganization must be below 0.1 mg/L [18]. Accordingly, the research
studies regarding the adsorption of cadmium ions by different adsor­
bents were continuously extended and reinforced. From all the proposed
materials, either natural or synthesized adsorbents, the layered double
hydroxides (LDHs) hold the attention of scientists.
Different reaserch teams communicated a detailed description of the
LDHs regarding the structure, general formula, methods of obtaining,
and advantages offered by using these materials [19–28].
LDHs have been synthesized mostly by the coprecipitation technique
at constant pH, which involves mixing two solutions, one consisting of
precursor salts of the bivalent and the trivalent metal ions and the other
of precipitating agents (Na2CO3, NaOH). After coprecipitating, by add­
ing them concurrently to the reaction vessel, the sample maturation
stage follows. The product separation can be done by filtration, whereas
the drying is done in the oven at a predetermined temperature and time.
By applying the heat treatment to LDHs, the calcined product is obtained
[29,30].
In the last years, research on magnetic particles appears to be a
branch of nanotechnology due to the possibility of their applicability in
various fields [31]. Linley and the co-workers, respectively Zaidi and
colleques [32,33] reported that the magnetic properties allow for their
effective separation by a magnetic field. The most used iron oxides re­
ported in the specialized literature are Fe3O4 (magnetite) and γ-Fe2O3
(maghemite), the co-precipitation method being the preferred method
in the synthesis of magnetic iron oxide nanoparticles [34,35].
The overall aim of this study was to develop an active magnetic
hybrid material with a high level of cadmium uptake based on MgAl
Layered Double Hydroxide (MgAl LDH) and magnetite (Fe3O4) for the
improvement of the life cycle of the magnetic light-weight structures
utilized in environmental remediation via optimization of the properties
of the 2D material and increasing adsorption capacities.
The obtained results on the preparation of highly dispersed 2D
magnetic hetero-sheets formed by the staggering accumulation of the
Fe3O4 on the surface of the MgAl-LDH fulfilled a series of specific ob­
jectives: (i) material characterization using advanced methods to gain a
better understanding and to propose new materials combinations; (ii)
adsorption performance evaluation by investigation of different working
parameters: pH, adsorbent dosage, contact time, initial Cd (II) concen­
tration; (iii) isotherm and kinetic modeling; (iii) desorption study; (iv) a
comparison with literature. The materials have not been identified as
hazardous; therefore, these findings might act as a base for future
research on low-cost adsorbent materials for green removing of cad­
mium ion from wastewaters.
2. Materials and methods
2.1. Materials
The chemical reagents were analytical grade and were used as
received. Mg(NO3)2 ⋅ 6H2O (Sigma Aldrich ≥98%), Al(NO3)3 ⋅ 9H2O
(ACS reagent ≥98%), NaOH (Sigma Aldrich, pellets (anhydrous ≥98%),
and Na2CO3 (Sigma Aldrich, ACS reagent, anhydrous, ≥99.5%, powder)
were used for the synthesis of the LDHs. Ferric chloride (FeCl3 ⋅ 6H2O,
ACS reagent ≥97%) and ferrous chloride (FeCl2 ⋅ 4H2O, ReagentPlus,
98%) salts were used for the synthesis of magnetite nanoparticles. A
series of flasks (100 mL) containing different Cd (II) concentrations were
prepared by diluting adequate volumes from a stock solution of 1000
mg/L. A solution of 0.1 M HNO3 (Sigma Aldrich, ACS reagent ≥90%)
was added to adjust the pH of the stock solution.
2.2. Synthesis of MgAl-LDH
MgAl-LDH was synthesized using the co-precipitation method at a
pH of 9.5. The solution of salts was prepared by dissolving Mg
(NO3)2⋅6H2O (0.126 mol) and Al (NO3)3⋅9H2O (0.063 mol) into deion­
ized water. Then, precipitating agents of Na2CO3 and NaOH were added
dropwise, until the value of the working pH was recorded. The white
precipitate was heated for 12 h at 65 ◦ C. The precipitate was filtered and
then washed with deionized water until neutral pH was reached. In the
last step, the obtained product was dried at 60 ◦ C for 24 h.
2.3. Synthesis of magnetite nanoparticles (Fe3O4)
Magnetite nanoparticles (Fe3O4) were obtained by a chemical co-
precipitation process of ferric chloride (Fe3+) and ferrous chloride
(Fe2+) salts. For synthesis, 0.72 g FeCl2⋅4H2O and 0.5 g FeCl3⋅6H2O were
dissolved in 25 ml of deionized water containing 1 ml HCl. After
filtration, the obtained solution was added under magnetic stirring (700
rpm) over 300 ml of distilled water (at 100 ◦ C). Then, 100 mL 10%
NaOH solution was added progressively with a flow rate of 10 mL/min,
the solution turning rapidly to black. After adding the NaOH solution,
the heating was stopped, but magnetic stirring continued until the
temperature of the solution dropped to 40–45 ◦ C. The obtained magnetic
nanoparticles were magnetically separated and washed with deionized
water until the pH became 6–6.5. For physical characterization and
catalytic tests, the nanoparticles were stored in distilled water at room
temperature.
2.4. Synthesis of MgAl-LDH/Magnetic Nanoparticle Composite
MgAl-LDH/Magnetic Nanoparticle Composite was obtained through
the same synthesis procedure as described above for magnetic nano­
particles, except for the ferrous chloride solution which was mixed with

2
D. Gherca et al. Materials Chemistry and Physics 284 (2022) 126047

Table 1 performed using the Wallis Zeta potential analyzer on the basis of laser
Summary of applied experimental conditions in adsorption process of Cd (II). doppler electrophoresis technology. The absorbance was determined by
pH Adsorbent Initial cadmium Time (min) the UV–Visible spectrophotometry method at 576 nm using PerkinElmer
dosage (g/L) concentration (mg/ Lambda 35 UV/VIS spectrophotometer. pH values were measured with a
L) digital pH meter (Hanna Instruments, Code HI 9024C).
2.5; 3.5; 5.0 1.4; 2.8; 4.2 100 ÷ 350 5 ÷ 180
adsorbent pH: 5, conc: pH: 5, adsorbent pH: 5, adsorbent 2.6. Adsorption experiments
dosage:1.4 g/L, 100 mg/L, dosage: 1.4 g/L, dosage: 1.4 g/L,
conc: 100 mg/L, time: 24 h time: 24 h conc: 200 mg/L
time: 24 h
Different influencing factors such as pH value, adsorbent dosage,
initial cadmium concentration, and contact time were investigated
(Table 1).
200 mg of MgAl-LDH and ultrasonicated before being adding over the The experiments were carried out in 15 mL capped polyethylene
ferric chloride solution. The material was abbreviated as Composite centrifuge tubes. Typically, a quantity of 14 mg of adsorbent was added
MgAl-LDH + Fe3O4. to 10 mL of cadmium solution, at room temperature for 24 h. In the
context of MgAl-LDH material, the adsorbent was separated by filtra­
2.5. Characterization methods tion, whereas the two magnetic materials were separated using an
external magnetic field (NdFeB permanent magnet). The cadmium
The morphology and the microstructural features of materials were concentration in the supernatant solution was measured using a UV–vis
examined by scanning electron microscopy (JEOL JSM-6390 equipped spectrophotometer at 576 nm using xylenol-orange. The adsorption
with an EDS detector). The crystallographic structure was investigated capacity (q, mg/g), and the adsorption efficiency (R,%) were calculated
using X-ray diffraction analysis. An X-ray diffractometer (Advance D8- through equations (1) and (2):
Bruker) with a monochromatic CuKα (λ = 1.54056 Å) radiation was (C0 − Ce )V
used, in Bragg-Brentano geometry. The samples were analyzed in an q= (1)
m
ambient atmosphere with a rate of 0.010 s− 1, over the 2θ = (5–70)
range, 40 kV/40 mA. The Fourier transform infrared spectroscopy (FT- (C0 − Ce )
R= x100 (2)
IR) was run on Jasco FT-IR-6100 spectrometric analyzer using KBr C0
pellets. The magnetization data were acquired on a Lake Shore 7410
vibrating sample magnetometer (VSM). The mean hydrodynamic where: C0 and Ce are the initial and equilibrium Cd (II) concentrations,
diameter and size distribution of the colloidal nanoparticles were mg/L; q is the amount of Cd (II) adsorbed onto adsorbent, mg/g; V is the
measured by dynamic light scattering (DLS) – Microtrac/Nanotrac252. volume of solution, L; and m is the quantity of adsorbent, g.
CHEMBET 3000 TPR/TPD was used for the measurement of the specific
area of the materials, while the Zeta potential determinations were

Fig. 1. FE-SEM of MgAl-Layered Double Hydroxide at different magnifications.

3
D. Gherca et al. Materials Chemistry and Physics 284 (2022) 126047

Fig. 2. FE-SEM of Fe3O4 magnetic nanoparticles at different magnifications.

Fig. 3. FE-SEM of MgAl-LDH + Fe3O4 composite at different magnifications.

3. Results and discussion mainly of MgAl nanosheets self-assembled by a numbers of thinned

3.1. Characterization of synthesized samples
The characterization of textural, structural, and magnetic properties
was performed by series of complementary techniques to elucidate the
relationship among physicochemical characteristics.
3.1.1. FE-SEM analysis
The representative FE-SEM images at different magnifications of
pristine MgAl-LDH sample are presented in Fig. 1a–d. The particles are
arranged in’’sand-rose’’ shape [36–39].
Textural analysis of the MgAl-LDH sample revealed a three-
dimensional (3D) hierarchical nanostructure (Fig. 1a) consisting
interconnected nano lamellas. The morphology of the pristine MgAl-
LDH sample reveals spherical micro aggregates of well defined self-
assembled nanoplates (Fig. 1a) and surfaces (Fig. 1c-d) with different
open-pore sizes. Despite the size and shape of the aggregates were
irregular, MgAl-LDH displayed a very good crystallization degree
(Fig. 5). In conclusion, 3D flower-like hierarchical morphology can be
produced in the strictly performed experimental conditions as presented
in the synthesis section.
The size and surface morphology of the Fe3O4 magnetic nano­
particles were presented in Fig. 2a-b. The pristine Fe3O4 nanoparticles
prepared by the coprecipitation route formed large agglomerates indi­
cating that the nanoparticles collide and stick together leading to fractal-
like clusters. As expected, aggregation of magnetite nanoparticles

4
D. Gherca et al. Materials Chemistry and Physics 284 (2022) 126047

Fig. 4. FTIR spectra of 3D Hierarchical MgAl-LDH, pristine Fe3O4 nano­ Fig. 5. Powder XRD diffractograms of MgAl-LDH, Fe3O4, and MgAl-LDH +
particles, and 2D magnetic nanocomposite MgAl-LDH + Fe3O4. Fe3O4 composite material.

advantage of easy magnetic separation. Meanwhile, as stated above the

Table 2 induced topological transformation of 3D Hierarchical MgAl layered
Vibration mode assignments of MgAl-LDH, Fe3O4, and Composite MgAl-LDH +
double hydroxides to highly dispersed 2D magnetic hetero-nanosheets
Fe3O4.
feature is also important to satisfy all the mandatory characteristics of
Sample Wavenumber Assignment removal of toxic metal ions from aqueous solution by adsorption.
(cm− 1)

MgAl-LDH 3453 O–H stretching vibration 3.1.2. Fourier Transform Infrared Spectroscopy (FT-IR) analysis
1635 H–O–H bending vibrations of adsorbed
The detailed surface functional groups of 3D Hierarchical MgAl-
water molecules
1366 COO bending Layered Double Hydroxide, pristine Fe3O4 nanoparticles, and 2D mag­
790 Me–O, O–Me–O, and Me–O–Me stretching netic nanocomposite MgAl-LDH + Fe3O4 were investigated by Fourier
671 vibrations (Me=Mg, Al) Transform Infrared Spectroscopy (FT-IR). The FT-IR spectra of 3D Hi­
543 erarchical MgAl-Layered Double Hydroxide, pristine Fe3O4 nano­
450
particles, and 2D magnetic nanocomposite MgAl-LDH + Fe3O4 are
Composite 3447 O–H stretching vibration
MgAl-LDH þ 1641 H–O–H bending vibrations of adsorbed presented in Fig. 4.
Fe3O4 water molecules The main spectral bands and the vibration mode assignments of
1357 COO bending investigated samples MgAl-LDH, Fe3O4, and Composite MgAl-LDH +
790 Me–O, O–Me–O, and Me–O–Me stretching
Fe3O4 respectively are summarized in Table 2.
596 vibrations (Me=Mg, Al, Fe)
450
As shown in the FT-IR spectra, a wide absorption band is found for all
Fe3O4 3434 O–H stretching vibration samples in the range 3434–3453 cm− 1 which may be assigned to the
1632 H–O–H bending vibrations of adsorbed stretching vibration of hydroxyl groups from water molecules. In the
water molecules magnetite sample, additional bands are located at 1632 cm− 1 and 1373
1373 O–H bending vibrations
cm− 1 assigned to water that has been adsorbed and bending mode of
580 Fe–O stretching vibrations
451 hydroxyl groups. Besides, the absorption bands in the low region of the
spectra, the peaks centered at 580-451 cm− 1 correspond to the specific
lattice Fe–O stretching vibrations which are present also in as-prepared
occurred since simple coprecipitation of ferrous and ferric ions in the composites as very strong bands owing to the considerably high content
absence of any surfactant leads to such results. According to Fig. 2 the of Fe3O4 in the matrix. According to the spectra of composite, the three
nanoparticles are quasi-spherical with not uniform distribution, having main absorptions centered around 1641, 1357, and 450–790 cm− 1 were
a mean size of 10 nm. observed, corresponding to vibration absorption mode of O–H bending
The FE-SEM images of MgAlDH + Fe3O4 composite (Fig. 3a–d) vibrations, COO− anion, and the absorption bands of Me–O, O–Me–O,
revealed that the 3D Hierarchical MgAl layered double hydroxides, as and Me–O–Me stretching vibrations (Me = Mg, Al, Fe), respectively,
presented in Fig. 1a–d, is topological transformed in 2D LDH nanosheets confirming that the MgAl-LDH + Fe3O4 nanocomposite contained the
covered with magnetic Fe3O4 nanoparticles. The magnetic Fe3O4 characteristics absorption band of both components.
nanoparticles retain a similar pristine quasi-spherical shape with the
same mean size compared with that of initially formed pristine Fe3O4 3.1.3. X-ray diffraction analysis
(Fig. 2 a-b). The highly dispersed 2D magnetic hetero-sheets are formed The XRD results presented in Fig. 5 consist of MgAl-LDH, Fe3O4, and
by the staggering accumulation of the Fe3O4 on the surface of the MgAl- MgAl-LDH + Fe3O4 powder patterns measured on a 2θ scale from 5◦ to
LDH. The above-mentioned topological transformation has a good 70◦ .
impact on the properties of the composite. The MgAlDH + Fe3O4 In MgAl-LDH diffractogram can be found all Bragg reflections spe­
nanocomposites demonstrated essentially higher adsorptions capacity. cific for hydrotalcite – [(Mg4Al2)(OH)12(CO3)(H2O)3]0.5 indexed under
This could be attributed to the modification of the MgAl-LDHs surface PDF code – 00-014-0191, with <003> as main crystallographic plane
with Fe3O4 nanoparticles and the increased surface area and the unique positioned at 11.63◦ . Fe3O4 powder pattern corresponds to magnetite

5
D. Gherca et al.
Fig. 6. Magnetization hysteresis loop of the LDH 3 versus pristine Fe3O4. Insets:
(a) in the top left details from the loop near-zero magnetic field are shown; (b)
the attraction effect of the magnetic field on magnetic MgAl-LDH + Fe3O4
composite is depicted in the bottom right. The magnetic fields are generated by
NdFeB magnets.
phase with inverse spinel structure, where half of Fe3+ occupies the
tetrahedral sites and the rest of Fe3+ and Fe2+ cation occupies the
octahedral sites. The diffractogram can be indexed under PDF code – 00-
019-0629, specific for a face-centered cubic structure with Fd-3m space-
group type. MgAl-LDH + Fe3O4 powder pattern possesses all the
representative reflections of MgAl-LDH and Fe3O4 phases, proving that
both materials were thoroughly synthesized [40–46]. The wt ratio
MgAl-LDH: Fe3O4 of 1 : 4 is to be noticed by comparing the specific
reflection intensities of MgAl-LDH and Fe3O4 phases in the MgAl-LDH +
Fe3O4 powder pattern.
3.1.4. Vibrating sample magnetometer (VSM) analysis
According to VSM analysis (see Fig. 6), the specific saturation
magnetization for Fe3O4 was 47.4 emu/g, whereas for MgAl-LDH +
Fe3O4 (noted LDH 3 in the vide infra figure) decreased to 35.2 emu/g,
indicating that the magnetic clay can be quickly separated by an
external magnetic field from the treated solution.
The field coercivity, Hc, and remanent magnetization, Mr, of the
MgAl-LDH + Fe3O4 particles, were 7.2 Oe and 0.4 emu/g, respectively,
while Fe3O4 increased by an order of magnitude, i.e. to 82.8 Oe and 5.8
emu/g, respectively. Therefore, the MgAl-LDH + Fe3O4 is close to a
Fig. 7. DLS analysis showing the size distribution of the MgAl-LDH, Fe3O4 and Composite MgAl-LDH + Fe3O4 (a) and Zeta potential showing the surface charges of
the MgAl-LDH, Fe3O4 and Composite MgAl-LDH + Fe3O4 (b).
6
Materials Chemistry and Physics 284 (2022) 126047
superparamagnetic behavior, indicating that after removal of the mag­
netic field, the particles separate very well from the field-induced
agglomeration in the aqueous media. On the other hand, if compared
with Fe3O4, the decrease with only 25% of the specific saturation
magnetization is an indirect indication of the high amount of magnetite
nanoparticles bound to the clay. To improve the absorbance capacity of
the magnetic MgAl-LDH + Fe3O4 composite, it appears that the weight
contribution of the non-magnetic component should be increased.
However, this comes with the side effect of decreasing the capacity of
the compound to be quickly magnetically separated from the solution.
Therefore, a compromise between the magnetic properties and absor­
bance capacity of the magnetic composite should be well established
and equilibrated in real up-scaled applications.
3.1.5. Dynamic light scattering (DLS), zeta potential and BET surface
analyses
To gain a better understanding over the mechanism of cadmium
adsorption improvement, all synthesized samples were subjected to
dynamic light scattering (Fig. 7a), Zeta potential (Fig. 7b) and BET
surface measurements (Table 3) in order to determine the hydrodynamic
diameter, size distribution, surface charges and specific surface area.
As presented in Fig. 7a DLS analysis showed mean sizes of the MgAl-
LDH and MgAl-LDH + Fe3O4 particles in micrometer range, with two
separate fractions, namely 1.32/0.35 μm for LDH and 0.94/0.17 μm, for
MgAl-LDH + Fe3O4. By contrary, a narrow size distribution was
measured for magnetite nanoparticles, with a mean size of 33 nm
(Fig. 7a). However, the mean sizes provided by the DLS method is
related to the hydrodynamic diameter of the particles and, therefore,
they seem bigger [47]. The surface charge can be determined by
measuring the zeta potential [48]. As shown in Fig. 7b, the colloidal
suspensions of the Fe3O4 (pH = 7.12) and of the composite MgAl-LDH +
Fe3O4 samples at pH = 7.13 showed negatively charged surfaces with
appropriate ξ-potential values of − 13.83 mv and − 15.05 mV, respec­
tively while the ξ-potential value of pristine MgAl-LDH sample (+46.06
mV) at pH = 7.45 was much positively than that of the composite. These
Table 3
The hydrodynamic diameter, surface charges and specific surface area of MgAl-
LDH, Composite MgAl-LDH + Fe3O4 and Fe3O4.
Sample DLS hydrodynamic ξ BET
diameter (nm) Zeta potential Surface Area
(mV) (m2 g− 1)
MgAl-LDH 1320 þ 46.06 31.78
Composite MgAl- 940 - 15.05 80.24
LDH þ Fe3O4
Fe3O4 33 - 13.83 n.a
D. Gherca et al.
Fig. 8. The adsorption capacity (a) and removal efficiency (b) of Cd (II) as a function of initial pH (adsorbent dosage: 1.4 g/L; initial Cd (II) concentration: 100 mg/L;
24 h contact time; room temperature).
Fig. 9. The adsorption capacity (a) and removal efficiency (b) of Cd (II) as a function of adsorbent dosage (pH: 5; initial Cd (II) concentration: 100 mg/L; 24 h contact
time; room temperature).
results indicates that the synergistic effect can be produced mainly
attributed to the modification of the MgAl-LDHs surface with Fe3O4
nanoparticles. The synergistic effect leads to the increased negatively
charged surface on the composite and thus providing unique advantage
of easy adsorption of divalent positive charged cadmium ions. Apart
from the net improvement of the zeta potential, the induced topological
transformation of 3D Hierarchical MgAl layered double hydroxides to
highly dispersed 2D magnetic hetero-nanosheets feature is also impor­
tant in regards to the specific surface area (Table 3) which was consid­
erably increased from 31.78 m2 g− 1 (MgAl-LDH) to 80.24 m2 g− 1
(Composite MgAl-LDH + Fe3O4). These features, togheter with all
properties will satisfy all the mandatory characteristics of removal of
toxic metal ions from aqueous solution by adsorption.
3.2. Removal performance of MgAl-LDH, Fe3O4, and MgAl-LDH + Fe3O4
composite material
3.2.1. Effect of pH
As a general rule, the pH of the solution is a very important
parameter that has an intense effect on both the adsorbent’s surface
charge and the ionic state of the heavy metal [49]). The effect of pH on
Cd (II) adsorption capacity by prepared adsorbents was determined at
pH values of 2.5, 3.5, and 5. The pH range over 5 was excluded from the
pH effect study due to risk of cadmium precipitation on adsorbents
surface. Other research teams discovered the same thing [8,50]. The
maximum adsorption occurred at pH 5 (Fig. 8); consequently this value
was used in the following experiments.
7
Materials Chemistry and Physics 284 (2022) 126047
As can be observed from Fig. 8, the adsorption capacities and the
removal efficiencies of all examined adsorbents increase as the pH value
increases. MgAl-LDH, Fe3O4, and Composite MgAl-LDH + Fe3O4 indi­
cate an increase from 9.4 mg/g (13.35%) to 25 mg/g (35.8%), 23 mg/g
(33.8%) to 28 mg/g (40.1%), and 42.9 mg/g (60.9%) to 63 mg/g
(90.1%). The adsorption efficiency increases with the increases in pH
value.
3.2.2. Effect of adsorbent dosage
The adsorption method requires the establishment of an optimum
adsorbent dosage. The adsorbent dosage is on other critical parameters
impacting the adsorbent efficiency.
A preliminary study regarding the effect of three different adsorbent
dosages was examined, Fig. 9. The values of 1.4 g/L, 2.8 g/L, and 4.2 g/L
adsorbent dosage were chosen in order to determine the influence of a
small quantity of LDH calcined versus a quantity three times higher.
The results revealed that the adsorption capacity depends largely on
the adsorbent dosage; thus, the maximum adsorption of Cd (II) ions was
achieved by using a quantity of 14 mg adsorbent while decreasing when
a double and triple quantity of adsorbent (28 mg, 42 mg) was used: from
25 mg/g to 17.2 mg/g for MgAl-LDH, from 28.2 mg/g to 13.8 mg/g for
Fe3O4, and 63.4 mg/g to 19 mg/g for Composite MgAl-LDH + Fe3O4,
respectively. A similar behavior was reported on Cd (II) ion adsorption
by Ofudje and colleagues [51].This difference obtained using different
amounts of adsorbent can be explained as a result that not all the
adsorption sites were used or perhaps due to the formation of some
particle agglomeration as a consequence of using substantial adsorbent
D. Gherca et al.
Fig. 10. The adsorption capacity of Cd (II) as a function of initial concentration: adsorption capacity (a) and removal efficiency (b) (pH: 5; adsorbent dosage: 1.4 g/L;
24 h contact time; room temperature).
Fig. 11. The adsorption capacity (a) and removal efficiency (b) of Cd (II) as a function of contact time (pH: 5; adsorbent dosage: 1.4 g/L; initial Cd (II) concentration:
200 mg/L; room temperature).
dosages. Thereby, an adsorbent dosage of 1.4 g/L was selected.
3.2.3. Effect of initial concentration
This is also an important parameter to examine when investigating
the adsorption of a potential adsorptive material. In order to study the
effect of initial Cd (II) concentration, the optimal conditions were
maintained (pH of 5.0, adsorbent dose of 1.4 g/L). The effect of this
parameter was studied at six different Cd (II) concentration from 100 to
350 mg/L (Fig. 10). The performance of all adsorbents in removing Cd
(II) is affected by the initial concentration. For MgAl-LDH, the adsorp­
tion efficiency increased from 35.8% (25 mg/g) for 100 mg/L to 39.8%
for 200 mg/L (56 mg/g), and decreased at 28.9% for 350 mg/L (71.3
mg/g).
For Composite MgAl-LDH + Fe3O4 for Cd (II) ions the adsorption
capacity increased from 63 to 107 mg/g, compared with Fe3O4 (from 28
to 67.8 mg/g). For all adsorbents, the increase in adsorption capacity
with an increase in Cd (II) ion concentration could be justified by the
existence of a larger quantity of Cd (II) ions in solution accessible for
conveying toward to the active sites of the material. The adsorption sites
are rapidly occupied at low Cd (II) concentrations. As the initial con­
centration of Cd (II) increased, the majority of the accessible adsorption
sites become no longer available, leading to a decrease in the removal
efficiency. As more adsorbates are adsorbed, a decrease of the accessible
sites on the adsorbent is obtained. Furthermore, at a concentration
above 250 mg/L of Cd (II), the adsorption capacity reached a saturation
plateau due a limited number of active sites of adsorbents or even to the
8
Materials Chemistry and Physics 284 (2022) 126047
saturation of the active sites.
3.2.4. Effect of contact time
A relatively short time to achieve equilibrium is very important if,
among other purposes, one desires to evaluate an adsorbent from the
standpoint of applicability in the treatment of wastewaters contami­
nated with heavy metals. Since the MgAl-LDH, Fe3O4, and Composite
MgAl-LDH + Fe3O4 materials need to meet the objective to be suitable
candidates as adsorbents in Cd (II) adsorption techniques, the effect of
contact time was studied at preset periods. The adsorption capacity and
also the removal efficiency increased initially quickly with time and then
slows as the reaction approached equilibrium. This finding was as well
pointed out by another researchers [4,52–54]. The adsorption equilib­
rium reached a steady state at 60 min with 55.2 mg/g (38.65%) for
MgAl-LDH, 41.2 mg/g (28.9) for Fe3O4, and 86.2 (60.31%) mg/g for
Composite MgAl-LDH + Fe3O4 (Fig. 11).
3.3. Adsorption kinetics
To better investigate the adsorption behavior, the pseudo-first-order
model, pseudo-second-order model (linear and nonlinear forms), and
intraparticle diffusion model were applied to analyze the obtained data
as shown in Fig. 12. The models can be expressed using Eq. (3) - Eq. (5).
Pseudo-first order model [55]:
(k1 t)
log(qe − qt ) = log qe − (3)
2.303
D. Gherca et al. Materials Chemistry and Physics 284 (2022) 126047

Fig. 12. Kinetic models.

Table 4
Adsorption kinetic parameters of Cd (II).
Adsorbent Experimental qe, mg/ Pseudo-first order Pseudo-second order model Intraparticle Intraparticle
g model diffusion diffusion
Linear Model Non-linear Model
Stage I Stage II

MgAl-LDH 55.2 k1 , 1/min = 0.08 qe cal, mg/g = 56.5 qe cal, mg/g = 59.4 KID = 6.05 KID = 0.06
R2 = 0.9886 k2 , g/mg.min = k2 , g/mg.min = A = 16.18 A = 54.5
0.005 0.0025 R2 = 0.8922 R2 = 0.6252
R2 = 0.9989 R2 = 0.9901
Fe3O4 41.2 k1 , 1/min = 0.105 qe cal, mg/g = 41.6 qe cal, mg/g = 42.31 KID = 2.19 KID = 0.007
R2 = 0.9142 k2 , g/mg.min = k2 , g/mg.min = A = 26.2 A = 41.09
0.014 0.008 R2 = 0.9873 R2 = 0.6251
R2 = 0.9997 R2 = 0.9987
Composite MgAl-LDH þ 86.2 k1 , 1/min = 0.109 qe cal, mg/g = 86.9 qe cal, mg/g = 89.68 KID = 6.04 KID = 0.02
Fe3O4 R2 = 0.9755 k2 , g/mg.min = k2 , g/mg.min = A = 48.03 A = 85.9
0.007 0.0033 R2 = 0.9866 R2 = 0.6251
R2 = 0.9997 R2 = 0.9970

9
D. Gherca et al. Materials Chemistry and Physics 284 (2022) 126047

Table 5
Adsorption isotherm constants and correlation coefficients adsorption of Cd (II).
Adsorbent Linear Models Non-linear Models

Langmuir Freundlich Temkin Redlich- Langmuir Freundlich Temkin Redlich-

Peterson Peterson

MgAl-LDH qmax (mg/g) = KF , (mg/g)/(L/mg) = bT = 36.67 ARP = 1.06 qmax (mg/g) = KF , (mg/g)/(L/mg) = BT = 36.67 ARP = 0.371
91.7 1.06 BT = 67.56 BRP = 0.2086 151.56 2.29 AT = 0.033 BRP = 0.4421
KL , L/g = 0.012 1/n = 0.79 AT = R2 = 0.3865 KL , L/g = 0.0041 1/n = 0.64 R2 = 0. R2 = 0.9695
R2 = 0.705 R2 = 0.9007 29.96 R2 = 0.8941 R2 = 0.848 9311
R2 =
0.9449
Fe3O4 qmax (mg/g) = KF , (mg/g)/(L/mg) = bT = 31.08 ARP = 1.57 qmax (mg/g) = KF , (mg/g)/(L/mg) = BT = 31.08 ARP =
80.6 1.52 BT = 79.71 BRP = 0.3144 184.52 1.32 AT = 0.035 242.101
KL , L/g = 0.012 1/n = 0.69 AT = 28.5 R2 = 0.7413 KL , L/g = 0.0025 1/n = 0.7215 R2 = BRP = 319.51
R2 = 0.732 R2 = 0.9316 R2 = R2 = 0.8965 R2 = 0.9001 0.8516 R2 = 0.8668
0.8812
MgAl-LDH þ qmax (mg/g) = KF , (mg/g)/(L/mg) = bT = 14.97 ARP = 41.07 qmax (mg/g) = KF , (mg/g)/(L/mg) = BT = 14.98 ARP =
Fe3O4 109.9 40.85 BT = 165.5 BRP = 0.8199 104.59 40.18 AT = 5.73 35143.62
KL , L/g = 0.105 1/n = 0.18 AT = 5.73 R2 = 0.9996 KL , L/g = 0.1236 1/n = 0.1852 R2 = BRP = 1.41E6
R2 = 0.991 R2 = 0.9925 R2 = R2 = 0.7823 R2 = 0.9899 0.9644 R2 = 0.9849
0.9733

Pseudo-second order model [56,57]:

Table 6
t 1 t Comparison of maximum capacity (qmax ) for different adsorbents for Cd (II)
Linear form : = + (4a)
qt k2 qe 2 qe adsorption.
Adsorbent qmax , mg/g Reference
k2 q2e t
Nonlinear form : qt = (4b) Fe3O4@APS@AA-co-CA 29.6 [70]
1 + k2 qe t A. sphaerica 111.1 [71]
MWCNTs 61.1 [72]
Intraparticle diffusion model [58]:
Halloysite-Fe3O4 3.96 [73]
qt = KID t0.5 + A (5) Bentonite-Fe3O4– MnO2 35.35 [74]
Fe3O4/SC 18.9 [75]
Ni/Mo-LDH 53.6 [76]
in which, qt (mg/g) is the amount of cadmium adsorbed at time t, qe Maifanite/MgAl-LDHs 3.77 [77]
(mg/g) is the amount of cadmium adsorbed at equilibrium, k1 is the KB/LDH 25.6 [78]
pseudo-first-order rate constant (min− 1), k2 is the pseudo-second-order Pristine biochar 1.78 [78]
rate constant (g mg− 1 min− 1); KID and A (mg/g) are the intraparticle MA-MNPs 81.6 [79]
Fe3O4–SO3H MNPs 80.9 [80]
diffusion unchanging factors.
Mg–Al–CO3-LDH 61.4–70.2 [81]
Kinetic data were explained through a pseudo-second-order model Magnetic Fe3O4/Mg–Al–CO3–LDH 45.6–54.7 [81]
(Table 4). Another indicator that supports this statement is that the Fe3O4 9.5 [82]
adsorption capacities at equilibrium are very close to those obtained MK 34.6 [60]
GEO-0.8, GEO-1.2, GEO-1.6, GEO-2.0 67.8; 47.1; [60]
experimentally [59–62].
39.8; 33.9 [67]
The pseudo-second order nonlinear model has also been shown to BC 19.3–34.8
successfully predict the kinetics of cadmium ion adsorption. BCS 41.1–48.9 [67]
FMBC 79 [83]
Tartaric acid modified rice husk (TARH). 45.5 [52]
3.4. Adsorption isotherms 2,4-Dinitrophenylhydrazine immobilized on 255 [84]
sodium dodecyl sulfate (SDS)-coated magnetite
MgAl-LDH 91.7 This
From all suggested adsorption isotherms, the experimental data were
study
fitted using Langmuir Freundlich, Temkin, and Redlich-Peterson Fe3O4 80.6 This
models, which are the most popular isotherms [58,63–68]. The study
adsorption isotherms calculated in linear and nonlinear forms [57] from Composite MgAl-LDH þ Fe3O4 109.9 This
study
the all models are presented in Table 5.
To establish which isotherm fits the data obtained, correlation co­
efficients, R2, were compared. According to the values of R2, the 3.6. Desorption study
Freundlich model is more suitable than the Langmuir model to describe
the adsorption capacity of cadmium ions onto MgAl-LDH and Fe3O4 Three cycles of adsorption/desorption were conducted in order to
adsorbents. According to the R2 values, for the Composite MgAl-LDH + gain vital information regarding the ability of the adsorbents to be
Fe3O4 the fits follow the order: Redelich-Peterson > Freundlich > reused. The adsorption/desorption cycles were carried out experimen­
Langmuir > Temkin. The Redelich-Peterson model shows the charac­ tally as follows: Cd (II) ion adsorption was carried out at pH 5; 1.4 g/L
teristics of both Langmuir and Freundlich isotherms and suggests a adsorbent dosage; initial Cd(II) concentration of 200 mg/L; temperature
“three-parameter model’’ [69]. = 25 ◦ C. The samples loaded with Cd (II) ion were treated with 0.1 M
HNO3 solution in desorption investigations. Three rounds of the oper­
ation were carried out and the experimental results are presented in
3.5. Comparison with other adsorbents
Fig. 13.
After three cycles of adsorption/desorption the adsorption capacity
The maximum adsorption capacities of Cd (II) on different adsor­
decreases from 55.2 mg/g to 49.62 mg/g for MgAl-LDH, from 41.41 mg/
bents are listed by comparison in Table 6. Extremely different values can
g to 36.81 mg/g for Fe3O4, and from 86.16 mg/g to 79.7 mg/g for
be observed depending on the studied material.

10
D. Gherca et al.
Fig. 13. The adsorption/desorption cycles carried out experimentally at pH 5;
1.4 g/L adsorbent dosage; initial Cd(II) concentration of 200 mg/L; tempera­
ture = 25 ◦ C. The samples loaded with Cd (II) ion were treated with 0.1 M
HNO3 solution in desorption investigations.
Composite MgAl-LDH + Fe3O4. This study yielded promising results for
the application of MgAl-LDH, Fe3O4, and Composite MgAl-LDH + Fe3O4
adsorbents for the adsorption of Cd (II) ion from wastewater.
3.7. Mechanism of adsorption
The adsorption process of Cd (II) ion may be explained by chemi­
sorption and electrostatic interaction between adsorbents surface charge
and the Cd (II) charge.
A proposed mechanism of adsorption for Composite MgAl-LDH +
Fe3O4 is depicted in Fig. 14.
Fig. 14. Mechanism of adsorption for Composite MgAl-LDH + Fe3O4.
11
Materials Chemistry and Physics 284 (2022) 126047
4. Conclusion and future perspectives
Besides the MgAl-LDH and Fe3O4 magnetic nanoparticles, dispersed
magnetic 2D hetero-nanosheets of type MgAlDH + Fe3O4 were suc­
cessfully fabricated through chemical co-precipitation processes. FE-
SEM images showed the topological transformation of 3D Hierarchical
MgAl-LDH to the 2D LDH nanosheets, in the presence of Fe3O4 nano­
particles, which are beneficial for the efficient removal of cadmium from
aqueous solution. The higher adsorption capacity of 2D MgAlDH +
Fe3O4 was attributed to the improvement of the MgAl-LDHs surface
covered with magnetic Fe3O4 nanoparticles and the increased surface
area. The adsorption capacity of all materials prepared was investigated
extensively by varying pHs, adsorbent dosage, concentration, and con­
tact time. The results showed that the adsorption capacity increased
with increasing solution pH up to 5 and decreased with the adsorbent.
The contact time required to reach the equilibrium is 60 min and the
kinetic modeling of the experimental data indicates that all the
adsorption processes are described by the pseudo-second-order kinetic
model. The adsorption of Cd (II) for MgAl-LDH and Fe3O4 adsorbents is
better modeled by the Freundlich approach in the studied concentration
range. On the other hand, for Composite MgAl-LDH + Fe3O4, the data
obeyed Redelich-Peterson models, with R2 value of 0.9996. Moreover,
the amount of Cd (II) ions adsorbed are strongly related to the type of
adsorbent and decrease as follows: Composite MgAl-LDH + Fe3O4 >
MgAl-LDH > Fe3O4. The findings underscore a good reusability of the
adsorbents after three cycles of adsorption/desorption. The materials
synthesized in this study are suitable candidates as adsorbents in Cd (II)
adsorption processes, with emphasis on the MgAl-LDH + Fe3O4, that
showed a high maximum adsorption capacity of 109.9 mg/g. The
application of Composite MgAl-LDH + Fe3O4 as an adsorbent for
different heavy metals (i.e. chromium, lead) and other categories of
pollutant, such as anionic/cationic dyes, will be the focus of future
research. A simultaneous removal will also be a challenge.
CRediT authorship contribution statement
Daniel Gherca: Conceptualization, Investigation, Methodology,
Writing – original draft, performed the experimental work, Formal
analysis, Resources, Software, Visualization, Writing – original draft.
D. Gherca et al.
Adrian Iulian Borhan: performed the experimental work, Formal
analysis, Resources, Software, Visualization, Writing – original draft.
Marius Mugurel Mihai: performed the experimental work, Formal
analysis, Resources, Software, Visualization, Writing – original draft.
Dumitru-Daniel Herea: performed the experimental work, Formal
analysis, Resources, Software, Visualization, Writing – original draft.
George Stoian: Formal analysis, Investigation FE-SEM analysis. Tiberiu
Roman: Investigation XRD analysis and interpreted the results and Co-
performed graphical design with Daniel Gherca. Horia Chiriac: Project
administration, Supervision, Validation, Writing – review & editing.
Nicoleta Lupu: Project administration, Supervision, Validation, Writing
– review & editing. Gabriela Buema: Conceptualization, Investigation,
Methodology, Writing – original draft, performed the experimental
work, Formal analysis, Resources, Software, Visualization, Writing –
original draft.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by a grant of the Ministry of Research,
Innovation and Digitization under the Nucleu programme, Project PN 19
28 01 01.
References
[1] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review,
J. Environ. Manag. 92 (2011) 407–418, https://doi.org/10.1016/j.
jenvman.2010.11.011.
[2] M. Amini, H. Younesi, N. Bahramifar, A.A.Z. Lorestani, F. Ghorbani, A. Daneshi,
M. Sharifzadeh, Application of response surface methodology for optimization of
lead biosorption in an aqueous solution by Aspergillus Niger, J. Hazard Mater. 154
(2008) 694–702, https://doi.org/10.1016/j.jhazmat.2007.10.114.
[3] S. Sobhanardakani, R. Zandipak, A. Javanshir-khoei, S.M. Hosseini, M. Moslemi,
P. Delfieh, Removal of Hg(II) and Cd(II) ions from aqueous solution using chitosan,
Kinetics Equilibrium Studies 3 (2015) 21–30.
[4] G. Buema, A.I. Borhan, D.D. Herea, G. Stoian, H. Chiriac, N. Lupu, T. Roman,
A. Pui, M. Harja, D. Gherca, Magnetic solid-phase extraction of cadmium ions by
hybrid self-assembled multicore type nanobeads, Polymer 13 (2021), https://doi.
org/10.3390/polym13020229.
[5] A.A. Alqadami, M. Naushad, M.A. Abdalla, T. Ahamad, Z. Abdullah ALOthman, S.
M. Alshehri, A.A. Ghfar, Efficient removal of toxic metal ions from wastewater
using a recyclable nanocomposite: a study of adsorption parameters and
interaction mechanism, J. Clean. Prod. 156 (2017) 426–436, https://doi.org/
10.1016/j.jclepro.2017.04.085.
[6] J. Ma, G. Qin, Y. Zhang, J. Sun, S. Wang, L. Jiang, Heavy metal removal from
aqueous solutions by calcium silicate powder from waste coal fly-ash, J. Clean.
Prod. 182 (2018) 776–782, https://doi.org/10.1016/j.jclepro.2018.02.115.
[7] R. Sahraei, Z. Sekhavat Pour, M. Ghaemy, Novel magnetic bio-sorbent hydrogel
beads based on modified gum tragacanth/graphene oxide: removal of heavy metals
and dyes from water, J. Clean. Prod. 142 (2017) 2973–2984, https://doi.org/
10.1016/j.jclepro.2016.10.170.
[8] G.K. Sarma, S. Sen Gupta, K.G. Bhattacharyya, Nanomaterials as versatile
adsorbents for heavy metal ions in water: a review, Environ. Sci. Pollut. Res. 26
(2019) 6245–6278, https://doi.org/10.1007/s11356-018-04093-y.
[9] Q.U. Ain, M.U. Farooq, M.I. Jalees, Application of magnetic graphene oxide for
water purification: heavy metals removal and disinfection, J. Water Proc. Eng. 33
(2020) 101044, https://doi.org/10.1016/j.jwpe.2019.101044.
[10] L. Shen, J. Wang, Z. Li, L. Fan, R. Chen, X. Wu, J. Li, W. Zeng, A high-efficiency
Fe2O3@Microalgae composite for heavy metal removal from aqueous solution,
J. Water Proc. Eng. 33 (2020) 101026, https://doi.org/10.1016/j.
jwpe.2019.101026.
[11] S. Wadhawan, A. Jain, J. Nayyar, S.K. Mehta, Role of nanomaterials as adsorbents
in heavy metal ion removal from waste water: a review, J. Water Proc. Eng. 33
(2020) 101038, https://doi.org/10.1016/j.jwpe.2019.101038.
[12] K.S. Rao, M. Mohapatra, S. Anand, P. Venkateswarlu, Review on cadmium removal
from aqueous solutions, Int. J. Eng. Sci. Technol. 2 (2010).
[13] S. Rastogi, B. Kandasubramanian, Progressive trends in heavy metal ions and dyes
adsorption using silk fibroin composites, Environ. Sci. Pollut. Res. 27 (2020)
210–237, https://doi.org/10.1007/s11356-019-07280-7.
[14] E. Kokkinos, K. Soukakos, M. Kostoglou, M. Mitrakas, Cadmium, mercury, and
nickel adsorption by tetravalent manganese feroxyhyte: selectivity, kinetic
12
Materials Chemistry and Physics 284 (2022) 126047
modeling, and thermodynamic study, Environ. Sci. Pollut. Res. 25 (2018)
12263–12273, https://doi.org/10.1007/s11356-017-9738-2.
[15] S. Sobhanardakani, Human health risk assessment of Cd, Cu, Pb and Zn through
consumption of raw and pasteurized cow’s milk, Iran, J. Public Health 47 (2018)
1172–1180.
[16] S. Sobhanardakani, R. Zandipak, Synthesis and application of TiO2/SiO2/Fe3O4
nanoparticles as novel adsorbent for removal of Cd(II), Hg(II) and Ni(II) ions from
water samples, Clean Technol. Environ. Policy 19 (2017) 1913–1925, https://doi.
org/10.1007/s10098-017-1374-5.
[17] R. Qiu, F. Cheng, H. Huang, Removal of Cd2+ from aqueous solution using
hydrothermally modified circulating fluidized bed fly ash resulting from coal
gangue power plant, J. Clean. Prod. 172 (2018) 1918–1927, https://doi.org/
10.1016/j.jclepro.2017.11.236.
[18] Lenntech water treatments, WHO’s drinking water standards, WHO’s Drink. Water
Stand, http://www.lenntech.com/applications/drinking/standards/who-s-drinkin
g-water-standards.htm, 2006, 1.
[19] S. Abelló, F. Medina, D. Tichit, J. Pérez-Ramírez, J.C. Groen, J.E. Sueiras,
P. Salagre, Y. Cesteros, Aldol condensations over reconstructed Mg-Al
hydrotalcites: structure-activity relationships related to the rehydration method,
Chem. Eur J. 11 (2005) 728–739, https://doi.org/10.1002/chem.200400409.
[20] P. Benito, F.M. Labajos, J. Rocha, V. Rives, Influence of microwave radiation on the
textural properties of layered double hydroxides, Microporous Mesoporous Mater.
94 (2006) 148–158.
[21] P. Benito, F.M. Labajos, V. Rives, Microwaves and layered double hydroxides: a
smooth understanding, Pure Appl. Chem. 81 (2009) 1459–1471, https://doi.org/
10.1351/PAC-CON-08-07-01.
[22] C. Del Hoyo, Layered double hydroxides and human health: an overview, Appl.
Clay Sci. 36 (2007) 103–121.
[23] P.V. dos Santos Lins, D.C. Henrique, A.H. Ide, C.L. de Paiva e Silva Zanta, L. Meili,
Evaluation of caffeine adsorption by MgAl-LDH/biochar composite, Environ. Sci.
Pollut. Res. 26 (2019) 31804–31811, https://doi.org/10.1007/s11356-019-06288-
3.
[24] K.H. Goh, T.T. Lim, Z. Dong, Application of layered double hydroxides for removal
of oxyanions: a review, Water Res. 42 (2008) 1343–1368, https://doi.org/
10.1016/j.watres.2007.10.043.
[25] T.P.F. Teixeira, S.I. Pereira, S.F. Aquino, A. Dias, Calcined layered double
hydroxides for decolorization of azo dye solutions: equilibrium, kinetics, and
recycling studies, Environ. Eng. Sci. 29 (2012) 685–692.
[26] K.L. Erickson, T.E. Bostrom, R.L. Frost, A study of structural memory effects in
synthetic hydrotalcites using environmental SEM, Mater. Lett. 59 (2005) 226–229.
[27] K. Zhu, Y. Gao, X. Tan, C. Chen, Polyaniline-Modified Mg/Al layered double
hydroxide composites and their application in efficient removal of Cr(VI), ACS
Sustain. Chem. Eng. 4 (2016) 4361–4369, https://doi.org/10.1021/
acssuschemeng.6b00922.
[28] X. Zhang, Y. Dou, C. Gao, C. He, J. Gao, S. Zhao, L. Deng, Removal of Cd (II) by
modified maifanite coated with Mg-layered double hydroxides in constructed rapid
infiltration systems, Sci. Total Environ. 685 (2019) 951–962.
[29] L. Lv, J. He, M. Wei, D.G. Evans, X. Duan, Factors influencing the removal of
fluoride from aqueous solution by calcined Mg-Al-CO3 layered double hydroxides,
J. Hazard Mater. 133 (2006) 119–128, https://doi.org/10.1016/j.
jhazmat.2005.10.012.
[30] M. He, J. Zhou, J. Chen, F. Zheng, D. Wang, R. Shi, Z. Guo, H. Wang, Q. Chen,
Fe3O4@carbon@zeolitic imidazolate framework-8 nanoparticles as
multifunctional pH-responsive drug delivery vehicles for tumor therapy in vivo,
J. Mater. Chem. B. (2015), https://doi.org/10.1039/c5tb01830g.
[31] D.D. Herea, L. Labusca, E. Radu, H. Chiriac, M. Grigoras, O.D. Panzaru, N. Lupu,
Human adipose-derived stem cells loaded with drug-coated magnetic nanoparticles
for in-vitro tumor cells targeting, Mater. Sci. Eng. C 94 (2019) 666–676, https://
doi.org/10.1016/j.msec.2018.10.019.
[32] S. Linley, T. Leshuk, F.X. Gu, Magnetically separable water treatment technologies
and their role in future advanced water treatment: a patent review, Clean - Soil,
Air, Water 41 (2013) 1152–1156, https://doi.org/10.1002/clen.201100261.
[33] N.S. Zaidi, J. Sohaili, K. Muda, M. Sillanpää, Magnetic field application and its
potential in water and wastewater treatment systems, Separ. Purif. Rev. 43 (2014)
206–240, https://doi.org/10.1080/15422119.2013.794148.
[34] Q. Chang, L. Zhu, Z. Luo, M. Lei, S. Zhang, H. Tang, Sono-assisted preparation of
magnetic magnesium-aluminum layered double hydroxides and their application
for removing fluoride, Ultrason. Sonochem. 18 (2011) 553–561, https://doi.org/
10.1016/j.ultsonch.2010.10.001.
[35] T. Sheng, Z. Zhang, Y. Hu, Y. Tao, J. Zhang, Z. Shen, J. Feng, A. Zhang, Adsorption
of phosphorus by using magnetic Mg–Al-, Zn–Al- and Mg–Fe-layered double
hydroxides: comparison studies and adsorption mechanism, Environ. Sci. Pollut.
Res. 26 (2019) 7102–7114, https://doi.org/10.1007/s11356-019-04191-5.
[36] D.G. Cantrell, L.J. Gillie, A.F. Lee, K. Wilson, Structure-reactivity correlations in
MgAl hydrotalcite catalysts for biodiesel synthesis, Appl. Catal. Gen. 287 (2005)
183–190, https://doi.org/10.1016/j.apcata.2005.03.027.
[37] T. Xiao, Y. Tang, Z. Jia, D. Li, X. Hu, B. Li, L. Luo, Self-assembled 3D flower-like Ni2
+-Fe3+ layered double hydroxides and their calcined products, Nanotechnology
20 (2009) 1–8, https://doi.org/10.1088/0957-4484/20/47/475603.
[38] L.E. Dartu, G. Carja, Z. Carmen, LDH as Environmentally Friendly , Matrices with
High Adsorption Properties Chapter 7 LDHs as Environmental-Friendly Matrices
with High Adsorptive Properties, 2016, p. 2741.
[39] M.V. Bukhtiyarova, A review on effect of synthesis conditions on the formation of
layered double hydroxides, J. Solid State Chem. 269 (2019) 494–506, https://doi.
org/10.1016/j.jssc.2018.10.018.
D. Gherca et al.
[40] A. Tsyganok, A. Sayari, Incorporation of transition metals into Mg-Al layered
double hydroxides: coprecipitation of cations vs. their pre-complexation with an
anionic chelator, J. Solid State Chem. 179 (2006) 1830–1841, https://doi.org/
10.1016/j.jssc.2006.03.029.
[41] K. Xing, H. Wang, L. Guo, W. Song, Z. Zhao, Adsorption of tripolyphosphate from
aqueous solution by Mg-Al-CO3-layered double hydroxides, Colloids Surfaces A
Physicochem. Eng. Asp. 328 (2008) 15–20, https://doi.org/10.1016/j.
colsurfa.2008.06.015.
∏
[42] L. Li, P. Liu, L. Zhang, D. Chen, Photophysical properties of donor- -acceptor azoic
chromophores adsorbed and intercalated into MgAlLDH, J. Solid State Chem. 198
(2013) 218–223, https://doi.org/10.1016/j.jssc.2012.09.018.
[43] D. Chen, Y. Li, J. Zhang, J.Z. Zhou, Y. Guo, H. Liu, Magnetic Fe 3O 4/ZnCr-layered
double hydroxide composite with enhanced adsorption and photocatalytic activity,
Chem. Eng. J. 185–186 (2012) 120–126, https://doi.org/10.1016/j.
cej.2012.01.059.
[44] E. Saievar Iranizad, Z. Dehghani, M. Nadafan, Nonlinear optical properties of
nematic liquid crystal doped with different compositional percentage of synthesis
of Fe3O4 nanoparticles, J. Mol. Liq. 190 (2014) 6–9, https://doi.org/10.1016/j.
molliq.2013.09.032.
[45] R. ran Shan, L. guo Yan, Y. ming Yang, K. Yang, S. jun Yu, H. qin Yu, B. cun Zhu,
B. Du, Highly efficient removal of three red dyes by adsorption onto Mg-Al-layered
double hydroxide, J. Ind. Eng. Chem. 21 (2015) 561–568, https://doi.org/
10.1016/j.jiec.2014.03.019.
[46] X. Zheng, F. Kang, X. Liu, H. Peng, JinYang Zhang, Carbon-coated Mg–Al layered
double oxide nanosheets with enhanced removal of hexavalent chromium, J. Ind.
Eng. Chem. 80 (2019) 53–64, https://doi.org/10.1016/j.jiec.2019.07.030.
[47] H. Bae, T. Ahmad, I. Rhee, Y. Chang, S.-U. Jin, S. Hong, Carbon-coated iron oxide
nanoparticles as contrast agents in magnetic resonance imaging, Nanoscale Res.
Lett. 7 (2012) 2–6, https://doi.org/10.1186/1556-276x-7-44.
[48] F. Noli, M. Kapnisti, G. Buema, M. Harja, Retention of barium and europium
radionuclides from aqueous solutions on ash-based sorbents by application of
radiochemical techniques, Appl. Radiat. Isot. (2016), https://doi.org/10.1016/j.
apradiso.2016.07.012.
[49] Z. Wang, L. Xu, D. Wu, S. Zheng, Hydrothermal synthesis of mesoporous
tobermorite from fly ash with enhanced removal performance towards Pb2+ from
wastewater, Colloids Surfaces A Physicochem. Eng. Asp. 632 (2022) 127775,
https://doi.org/10.1016/j.colsurfa.2021.127775.
[50] A.N. Amro, M.K. Abhary, M.M. Shaikh, S. Ali, Removal of lead and cadmium ions
from aqueous solution by adsorption on a low-cost Phragmites biomass, Processes
7 (2019), https://doi.org/10.3390/pr7070406.
[51] E.A. Ofudje, I.A. Adeogun, M.A. Idowu, S.O. Kareem, N.A. Ndukwe, Simultaneous
removals of cadmium(II) ions and reactive yellow 4 dye from aqueous solution by
bone meal-derived apatite: kinetics, equilibrium and thermodynamic evaluations,
J. Anal. Sci. Technol. 11 (2020), https://doi.org/10.1186/s40543-020-0206-0.
[52] S. Sobhanardakani, R. Zandipak, Adsorption of Ni (II) and Cd (II) from aqueous
solutions using modified rice husk, Iran, J. Health Sci. 43 (2015) 92–96.
[53] N. Popa, M. Visa, New hydrothermal charcoal TiO2 composite for sustainable
treatment of wastewater with dyes and cadmium cations load, Mater. Chem. Phys.
258 (2021) 123927, https://doi.org/10.1016/j.matchemphys.2020.123927.
[54] K. Hachem, D. Bokov, M.D. Farahani, B. Mehdizade, A.A. Kazemzadeh Farizhandi,
Ultrasound-assisted adsorption of dyes and cadmium ion from aqueous solutions by
ZnAl2O4 nanoparticles, Mater. Chem. Phys. 276 (2022) 125398, https://doi.org/
10.1016/j.matchemphys.2021.125398.
[55] S. Lagergren, Zur Theorie der Sogenannten adsorption Gelöster stoffe, Bidr. till K.
Sven. Vetenskapsakademiens Hist. 24 (1898) 1–39.
[56] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (1999) 451–465, https://doi.org/10.1016/S0032-9592(98)00112-5.
[57] J. López-Luna, L.E. Ramírez-Montes, S. Martinez-Vargas, A.I. Martínez, O.
F. Mijangos-Ricardez, M. del C.A. González-Chávez, R. Carrillo-González, F.
A. Solís-Domínguez, M. del C. Cuevas-Díaz, V. Vázquez-Hipólito, Linear and
nonlinear kinetic and isotherm adsorption models for arsenic removal by
manganese ferrite nanoparticles, SN Appl. Sci. 1 (2019) 1–19, https://doi.org/
10.1007/s42452-019-0977-3.
[58] A.H. Omidi, M. Cheraghi, B. Lorestani, S. Sobhanardakani, A. Jafari, The biochars
prepared from cinnamon and cannabis as nature-friendly adsorbents for removal of
Cd(II) ions from aqueous solutions, SN Appl. Sci. 2 (2020) 1–13, https://doi.org/
10.1007/s42452-020-2954-2.
[59] C. Zou, W. Jiang, J. Liang, X. Sun, Y. Guan, Removal of Pb(II) from aqueous
solutions by adsorption on magnetic bentonite, Environ. Sci. Pollut. Res. 26 (2019)
1315–1322, https://doi.org/10.1007/s11356-018-3652-0.
[60] T. Lan, P. Li, F.U. Rehman, X. Li, W. Yang, S. Guo, Efficient adsorption of Cd2+
from aqueous solution using metakaolin geopolymers, Environ. Sci. Pollut. Res. 26
(2019) 33555–33567, https://doi.org/10.1007/s11356-019-06362-w.
[61] S.M. Ibrahim, A.A. Badawy, H.A. Essawy, Improvement of dyes removal from
aqueous solution by Nanosized cobalt ferrite treated with humic acid during
coprecipitation, J. Nanostructure Chem. 9 (2019) 281–298, https://doi.org/
10.1007/s40097-019-00318-9.
[62] Y.H. Jiang, A.Y. Li, H. Deng, C.H. Ye, Y. Li, Phosphate adsorption from wastewater
using ZnAl-LDO-loaded modified banana straw biochar, Environ. Sci. Pollut. Res.
26 (2019) 18343–18353, https://doi.org/10.1007/s11356-019-05183-1.
13
Materials Chemistry and Physics 284 (2022) 126047
[63] M. Changmai, M.K. Purkait, Kinetics, equilibrium and thermodynamic study of
phenol adsorption using NiFe2O4 nanoparticles aggregated on PAC, J. Water Proc.
Eng. 16 (2017) 90–97, https://doi.org/10.1016/j.jwpe.2016.12.011.
[64] I. Maulana, F. Takahashi, Cyanide removal study by raw and iron-modified
synthetic zeolites in batch adsorption experiments, J. Water Proc. Eng. 22 (2018)
80–86, https://doi.org/10.1016/j.jwpe.2018.01.013.
[65] M. Song, M. Li, Adsorption and regeneration characteristics of phosphorus from
sludge dewatering filtrate by magnetic anion exchange resin, Environ. Sci. Pollut.
Res. 26 (2019) 34233–34247, https://doi.org/10.1007/s11356-018-4049-9.
[66] Y. Liu, J. Luan, C. Zhang, X. Ke, H. Zhang, The adsorption behavior of multiple
contaminants like heavy metal ions and p-nitrophenol on organic-modified
montmorillonite, Environ. Sci. Pollut. Res. (2019) 10387–10397, https://doi.org/
10.1007/s11356-019-04459-w.
[67] W. Yin, C. Zhao, J. Xu, Enhanced adsorption of Cd (II) from aqueous solution by a
shrimp bran modified Typha orientalis biochar, Environ. Sci. Pollut. Res. 26 (2019)
37092–37100, https://doi.org/10.1007/s11356-019-06658-x.
[68] H. Alyasi, H.R. Mackey, K. Loganathan, G. McKay, Adsorbent minimisation in a
two-stage batch adsorber for cadmium removal, J. Ind. Eng. Chem. 81 (2020)
153–160, https://doi.org/10.1016/j.jiec.2019.09.003.
[69] R. Singh, R. Bhateria, Optimization and experimental design of the Pb2+
adsorption process on a nano-Fe3O4-based adsorbent using the response surface
methodology, ACS Omega 5 (2020) 28305–28318, https://doi.org/10.1021/
acsomega.0c04284.
[70] F. Ge, M.M. Li, H. Ye, B.X. Zhao, Effective removal of heavy metal ions Cd 2+, Zn 2
+, Pb 2+, Cu 2+ from aqueous solution by polymer-modified magnetic
nanoparticles, J. Hazard Mater. 211–212 (2012) 366–372, https://doi.org/
10.1016/j.jhazmat.2011.12.013.
[71] A.M. Abdel -Aty, N.S. Ammar, H.H. Abdel Ghafar, R.K. Ali, Biosorption of cadmium
and lead from aqueous solution by fresh water alga Anabaena sphaerica biomass,
J. Adv. Res. 4 (2013) 367–374, https://doi.org/10.1016/j.jare.2012.07.004.
[72] M. Hadavifar, N. Bahramifar, H. Younesi, M. Rastakhiz, Q. Li, J. Yu, E. Eftekhari,
Removal of mercury (II) and cadmium (II) ions from synthetic wastewater by a
newly synthesized amino and thiolated multi-walled carbon nanotubes, J. Taiwan
Inst. Chem. Eng. 67 (2016) 397–405.
[73] P. Maziarz, J. Matusik, Halloysite composites with Fe3O4Particles: the effect of
impregnation on the removal of aqueous Cd(II) and Pb(II), Mineralogia 48 (2016)
107–126, https://doi.org/10.1515/mipo-2017-0014.
[74] J. Liying, Q. Ye, J. Chen, Z. Chen, Y. Gu, Preparation of magnetically recoverable
bentonite–Fe3O4–MnO2 composite particles for Cd(II) removal from aqueous
solutions, J. Colloid Interface Sci. 513 (2018) 748–759, https://doi.org/10.1016/j.
jcis.2017.11.063.
[75] N. Kataria, V.K. Garg, Green synthesis of Fe3O4 nanoparticles loaded sawdust
carbon for cadmium (II) removal from water: regeneration and mechanism,
Chemosphere 208 (2018) 818–828, https://doi.org/10.1016/j.
chemosphere.2018.06.022.
[76] M.S. Mostafa, A.S.A. Bakr, Adsorptive removal of Cd(II) from contaminated water
via hexavalent molybdenum-containing layered double hydroxide: Ni/Mo-LDH,
Energy Sources, Part A Recover, Util. Environ. Eff. 41 (2019) 2257–2265, https://
doi.org/10.1080/15567036.2018.1555629.
[77] X. Zhang, Y. Dou, C. Gao, C. He, J. Gao, S. Zhao, L. Deng, Removal of Cd(II) by
modified maifanite coated with Mg-layered double hydroxides in constructed rapid
infiltration systems, Sci. Total Environ. 685 (2019) 951–962, https://doi.org/
10.1016/j.scitotenv.2019.06.228.
[78] Y. Tan, X. Yin, C. Wang, H. Sun, A. Ma, G. Zhang, N. Wang, Sorption of cadmium
onto Mg-Fe layered double hydroxide (LDH)-Kiwi branch biochar, Environ. Pollut.
Bioavailab. 31 (2019) 189–197, https://doi.org/10.1080/
26395940.2019.1604165.
[79] S. Ghafoor, S. Ata, Synthesis of Carboxyl-modified Fe3O4@SiO2 nanoparticles and
their utilization for the remediation of cadmium and nickel from aqueous solution,
J. Chil. Chem. Soc. 62 (2017) 3588–3592, https://doi.org/10.4067/s0717-
97072017000303588.
[80] K. Chen, J. He, Y. Li, X. Cai, K. Zhang, T. Liu, Y. Hu, D. Lin, L. Kong, J. Liu, Removal
of cadmium and lead ions from water by sulfonated magnetic nanoparticle
adsorbents, J. Colloid Interface Sci. 494 (2017) 307–316.
[81] R. ran Shan, L. guo Yan, K. Yang, Y. feng Hao, B. Du, Adsorption of Cd(II) by Mg-Al-
CO3- and magnetic Fe3O4/Mg-Al-CO3-layered double hydroxides: kinetic,
isothermal, thermodynamic and mechanistic studies, J. Hazard Mater. 299 (2015)
42–49, https://doi.org/10.1016/j.jhazmat.2015.06.003.
[82] M. Hosseinzadeh, S. Ali Seyyed Ebrahimi, S. Raygan, S. Morteza Masoudpanah,
Removal of cadmium and lead ions from aqueous solution by nanocrystalline
magnetite through mechanochemical activation, J. Ultrafine Grained Nanostruct.
Mater. 49 (2016) 72–79, https://doi.org/10.7508/jufgnsm.2016.02.03.
[83] C. Sun, T. Chen, Q. Huang, J. Wang, S. Lu, J. Yan, Enhanced adsorption for Pb(II)
and Cd(II) of magnetic rice husk biochar by KMnO4 modification, Environ. Sci.
Pollut. Res. 26 (2019) 8902–8913, https://doi.org/10.1007/s11356-019-04321-z.
[84] S. Sobhanardakani, R. Zandipak, 2,4-Dinitrophenylhydrazine functionalized
sodium dodecyl sulfate-coated magnetite nanoparticles for effective removal of Cd
(II) and Ni(II) ions from water samples, Environ. Monit. Assess. 187 (2015),
https://doi.org/10.1007/s10661-015-4635-y.