sustainability

Article
One-Step Fabrication of Amino-Functionalized Fe3O4@SiO2
Core-Shell Magnetic Nanoparticles as a Potential Novel
Platform for Removal of Cadmium (II) from Aqueous Solution
Deivasigamani Prabu 1 , Ponnusamy Senthil Kumar 2,3, * , Sravya Indraganti 2,3 , Sundararaman Sathish 1 ,
Jagadeesan Aravind Kumar 4 and Kabali Vijai Anand 5

1 Department of Chemical Engineering, Sathyabama Institute of Science and Technology,

Chennai 600119, India; [email protected] (D.P.); [email protected] (S.S.)
2 Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering,
Chennai 603110, India; [email protected]
3 Centre of Excellence in Water Research (CEWAR), Sri Sivasubramaniya Nadar College of Engineering,
Chennai 603110, India
4 Institute of Energy and Environmental Engineering, Saveetha School of Engineering, SIMATS,
Chennai 602105, India; [email protected]
5 Department of Physics, Sathyabama Institute of Science and Technology, Chennai 600119, India;
[email protected]
* Correspondence: [email protected]

Abstract: Fe3 O4 @SiO2 -NH2 core-shell magnetic nanoparticles were developed by a rapid one-step



precipitation route followed by reverse microemulsion and amine functionalization. In this study,


an Fe3 O4 @SiO2 -NH2 nanoparticle was used to evaluate its adsorption efficiency for the treatment
Citation: Prabu, D.; Senthil Kumar, P.;
of a synthetic solution of Cd(II) ion. The structural and physicochemical properties of Fe3 O4 @SiO2 -
Indraganti, S.; Sathish, S.; Aravind
NH2 nanoparticles were characterized by XRD, SEM-EDAX, TEM, FTIR and TGA. From the TEM
Kumar, J.; Vijai Anand, K. One-Step
analysis, the morphology of Fe3 O4 @SiO2 -NH2 was found as 100–300 nm. In TGA, the first weight
Fabrication of Amino-Functionalized
Fe3 O4 @SiO2 Core-Shell Magnetic
loss was noticed between 373 and 573 K, the second was between 673 and 773 K and the final weight
Nanoparticles as a Potential Novel loss took place above 773 K. Batch experimental tests, such as pH, dosage of Fe3 O4 @SiO2 -NH2 ,
Platform for Removal of Cadmium Cd(II) ion concentration, temperature as well as interaction time, were conducted and evaluated.
(II) from Aqueous Solution. Experimental study data were used for the non-linear forms exhibited by isotherms and kinetics of
Sustainability 2022, 14, 2290. the sorption procedure. The equilibrium adsorption observations were adequately combined with
https://doi.org/10.3390/su14042290 pseudo-first-order kinetics as well as Freundlich isotherm. Monolayer maximum adsorption capacity
Academic Editors: Chih-Chun Hsieh,
was found to be 40.02 mg/g, recorded at pH 6 with an interaction time of 30 min, temperature of
Jun-Yen Uan and Meng-Chang Lin 303 K and sorbent dose of 2.0 g/L. The thermodynamic study indicated that the adsorption process
was an exothermic, spontaneous reaction (−∆oo = −15.46–7.81 (kJ/mol)). The as-synthesized sorbent
Received: 25 December 2021
had excellent recyclability, and its adsorption efficiency was maintained after five cycles of reuse.
Accepted: 11 February 2022
The findings of the study exhibited the magnetic Fe3 O4 @SiO2 -NH2 -nanoparticle as an alternative
Published: 17 February 2022
effective adsorbent in eradicating Cd(II) ions from aqueous solution.
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in Keywords: magnetic nanoparticles; surface functionalization; Cd(II) ion adsorption; modeling; mechanism
published maps and institutional affil-
iations.

1. Introduction
Copyright: © 2022 by the authors.
Water scarcity is one of the world’s biggest problems with respect to the environ-
Licensee MDPI, Basel, Switzerland. ment. With advancements in urbanization and industrialization, the water environment
This article is an open access article gets polluted by the direct liberation of toxic pollutants, which results in heavy metal
distributed under the terms and contamination [1,2]. A huge amount of non-biodegradable heavy metals that have not been
conditions of the Creative Commons treated, for example, copper, cadmium, nickel, arsenic, mercury, lead ions and chromium,
Attribution (CC BY) license (https:// are discharged from the leather, textile, pigments, paper, glass, steel making, electroplat-
creativecommons.org/licenses/by/ ing, battery, mining operations and pharmaceutical sectors [3,4]. These heavy metals are
4.0/). discharged directly into the soil and water streams. Additionally, they also cause serious

Sustainability 2022, 14, 2290. https://doi.org/10.3390/su14042290 https://www.mdpi.com/journal/sustainability

Sustainability 2022, 14, 2290 2 of 21

health effects for aquatic systems and human beings. Heavy metals fall under the category
of non-biodegradable metals and are consistent, accumulate in nature and are poisonous
even in trace amounts [5]. Cadmium is one of the most toxic heavy metals, causing severe
effects on health, such as nausea, abdominal pain, pancreatic cancer, muscle cramps, vom-
iting and kidney damage. Significant sources of cadmium are the burning of fossil fuels,
manufacturing of phosphate fertilizers, metals, batteries, pigments and electroplating [6,7].
The permissible cadmium limit in consumable water is 0.003 mg/L, as per the Bureau of
Indian Standards (BIS) [8].
The use of conventional methodologies, such as biological techniques, bioremediation,
chemical precipitation and flocculation, have been widely used for removing these ions
from wastewater. Conventional methods have impediments, such as tedious usage of
power, equipment cost, secondary pollution and reusing issues relying on metals [9].
Innovative advancements, like magnetic separation techniques, are used to solve these
problems. Advancements in magnetic materials exploit their potential in various areas,
such as material synthesis, biology, environmental protection and textiles [10,11].
At present, magnetic nanoparticles (MNPs) have indicated a more significant role
in complete toxic heavy metal removal from wastewater. MNPs have favorable circum-
stances, for example, huge evacuation limits, high reactivity, high surface area as well as
fast kinetics [12–14]. In any case, the two most striking difficulties of the MNPs are that
they are more susceptible towards oxidation processes as well as the process of agglom-
eration bringing about difficult reusing, lessening the reaction works and surface area
constraints [15,16]. Considering these issues, novel multifunctional magnetic adsorbents
with an expanded number of active sites and less auxiliary contamination and poisonous
quality have come into the image. Mesoporous silica nanoparticles have a high surface area
and are progressively suitable in surface change, favoring improved expulsion of heavy
metal ions [17].
The primary issue related to mesoporous silica nanoparticles is the trouble in reusing
them and their inclination to aggregation. The core-shell nanoparticles comprise magnetic
nanoparticles as a center and external shell silica coating [18]. This empowers better recu-
peration and separation by the magnet. Nevertheless, the core-shell magnetic nanoparticles
have been accounted for as biocatalysts. To expand the expulsion effectiveness of the meso-
porous nanoparticles for metal evacuation, the surfaces of the nanoparticles were changed
by chemical functional groups. In addition, the hydroxyl group present in the silica coating
gives tremendous reaction sites for the amino functionalization of magnetic nanoparti-
cles [19]. Meanwhile, amino groups can work like chelation sites. Hence, molecules
containing amino groups can adsorb several metal-positive ions and are capable of being
used as adsorbents. The use of superparamagnetic iron oxide nanoparticles (SPIONs) with
surface modification possesses a high specific surface area [20]. SPIONs are extraordi-
narily affected by an external magnetic field. Adsorbents with magnetic properties can
be recovered and reused many times, thereby being considered environmentally friendly
substances [21,22].
In this work, amino-functionalized silica-coated core-shell magnetic nanoparticles
(Fe3 O4 @SiO2 -NH2 ) were employed as a novel efficient adsorbent for the removal of Cd(II)
from simulated water. The quality of the prepared material was identified through its
properties and experimental approach on the removal of Cd(II) ions. Various characteri-
zation methods, including scanning electron microscopy (SEM), X-ray diffraction (XRD),
transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), thermo-
gravimetric analysis (TGA) as well as Fourier transform infrared spectrophotometry (FTIR),
were performed in evaluating the diffraction index, elemental composition and chemical
composition of the nanocomposite. The adsorption experiments were directed in batch
mode, concerning dependent quantities like Cd(II) ion concentration, pH, interaction time,
a dose of Fe3 O4 @SiO2 -NH2 nanoparticle and temperature, and their optimum values were
assessed. The adsorption interaction behavior between the Fe3 O4 @SiO2 -NH2 nanoparticles
and Cd(II) ions was investigated by analyzing sorption kinetics and an isotherm model. Ad-
Sustainability 2022, 14, 2290 3 of 21

sorption mechanisms and thermodynamics of Cd(II) ion adsorption onto Fe3 O4 @SiO2 -NH2
were also investigated. Regeneration and reusability of the Fe3 O4 @SiO2 -NH2 were also
studied by adsorption regeneration cycles.

2. Experimental Study
2.1. Materials
Iron (III) chloride hexahydrate (FeCl3 ·6H2O), iron (II) sulfate heptahydrate (FeSO4 ·7H2 O),
oleic acid (OA), ammonium hydroxide (NH4 OH, 28%), tetra ethoxy silane (TEOS), 3-
aminopropyl trimethoxysilane (APS), Triton X-100, cyclohexane, ethanol and n-hexanol
were procured as analytical grade reagents from Loba Chemie India.

2.2. Preparation of Synthetic Cd(II) Ion Solution

Stock cadmium ion (100 mg/L) solution was made by mixing the calculated quantity of
cadmium sulfate octahydrate (3CdSO4 ·8H2 O) (Merck, India) using DI water. The required
test solutions (25–150 mg/L) were formed by using stock cadmium ion solution. The pH of
the initial solution was modified with 0.1 M NaOH or 0.1 M HCl solutions utilizing a pH
meter device (Elico Model) before mixing with adsorbent. Concentration readings of Cd(II)
ions were recorded utilizing an atomic absorption spectrometer (AAS, SL176 Model, Elico
Limited, Chennai, India). The deionized (DI) water was used for all purposes.

2.3. Preparation of Fe3 O4 @SiO2 -NH2 Nanoparticles

2.3.1. Synthesis of Oleic Acid Stabilized Fe3 O4 Nanoparticles
Oleic acid stabilized Fe3 O4 nanoparticles were synthesized by the co-precipitation
method, which depends upon the concentration of oleic acid. Approximately 11.6 g of
FeCl3 ·6H2 O and 4.3 g of FeSO4 ·7H2 O, dispersed with 400 mL DI water in a nitrogen
atmosphere with vigorous agitation at 333 K. After that, the 15 mL of 25% ammonia
solution was added, followed by quick dropwise mixing of the 9 mL oleic acid. The
resultant solution was centrifuged for 10 min at 6000 rpm to separate the black precipitates
of Fe3 O4 nanoparticles [23]. The final solid was flushed several times using DI water as
well as anhydrous ethanol to eliminate the excess oleic acid.

2.3.2. Preparation of Core-Shell Fe3 O4 @SiO2 Nanoparticles

The obtained oleic acid stabilized Fe3 O4 nanoparticles were then modified with silica
by following steps. First, the mixture of 500 µL of oleic acid, 50 mL of cyclohexane, 8 mL
of n-hexanol, 10 mL of TritonX-100, stabilized magnetic nanoparticles stock solution were
added with 500 µL of TEOS in a flask, and the resulting solution agitated vigorously. After
30 min of stirring, homogeneous microemulsions were formed. The resultant mixture was
added with 150 µL aqueous ammonia to initiate the polymerization reaction [24]. After 24 h
of continuous stirring, the silica growth was completed. The black precipitate Fe3 O4 @SiO2
nanoparticles were collected by the magnetic separation technique. Finally, the obtained
Fe3 O4 @SiO2 nanoparticles were flushed many times using ethanol, as well as water to
remove the excess solvents.

2.3.3. Functionalization of Fe3 O4 @SiO2 Nanoparticles

To achieve amino-functionalization of silica-coated magnetic nanoparticles (i.e.,
Fe3 O4 @SiO2 -NH2 ), 2 mL of 3-aminopropyl trimethoxysilane (APS) were added to the
95 mL ethanol solution. Then, the obtained dispersion was stirred for 3 h at 353 K. The
amino silane-functionalized magnetic nanoparticles were gathered by a bar magnet. The
resultant nanoparticles were washed many times with DI water [25]. Finally, the obtained
material was designated as Fe3 O4 @SiO2 -NH2 nanoparticles. The nanoparticles were dried
using vacuum on 353 K for approximately 12 h. The scheme of preparation of Fe3 O4 @SiO2 -
NH2 nanoparticles is shown in Figure 1.
Sustainability 2022, 14, 2290 4 of 21

Figure 1. Scheme of preparation route of Fe3 O4 @SiO2 -NH2 nanoparticles.

2.4. Characterization of Fe3 O4 @SiO2 -NH2 Nanoparticles

The morphological and size determination for Fe3 O4 @SiO2 -NH2 nanoparticles were
analyzed utilizing scanning electron microscope (SEM-EDAX, Hitachi S-3400 Model, Tokyo,
Japan) and HR-transmission electron microscope (JEOL JEM2010, HR-TEM, at 200 kV)
analyses. The specimens were made ready by dehydrating the samples and placing them
on 300 mesh copper grids coated with carbon. XRD investigation was conducted to
understand the chemical composition of Fe3 O4 @SiO2 -NH2 with an XRD analysis sampler,
Rikagu laboratory equipment, India, operating voltage of 40 kV, current recorded value
26 MA Cu-Kα2 radiations. FTIR analysis was carried out using amine-functionalized silica-
coated magnetic nanoparticles (0.01 g) dehydrated through the night at 333 K, blended
with 0.1 g of KBr. The obtained sample was used to check the moieties by FTIR spectra
(Shimadzu 8201PC, Kyoto, Japan). In order to investigate the magnetic properties of
synthesized Fe3 O4 @SiO2 -NH2 nanoparticles, particles were dispersed into distilled water
in a conical flask. A permanent magnet was kept next to the flask to ensure magnetic
separation. In addition, magnetic measurements were performed on the desired conditions
of temperature utilizing a vibrating magnetometer sample (VSM, 735VSM, Modl 7410;
lake Shore, Westerville, OH, USA) with a peak magnetic field of 31 kOe. Thermal stability
was performed to interpret the weight loss strategy utilizing a thermogravimetric analyzer
(model Q600 SDT simultaneous DSC–TGA) and heating rate of 283 K per minute under
N2 gas, carried out at 303–1073 K.

2.5. Batch Adsorption Study

Adsorption behavior exhibited by attractive Fe3 O4 @SiO2 -NH2 nanoparticles toward
Cd(II) ions was explored by batch studies. Under controlled conditions, the adsorp-
tion nature was studied at different parameters, e.g., initial metal ion concentrations
(25–150 mg/L), adsorbent quantity (0.5–3.0 g/L), temperature (303–333 K), pH (2.0–8.0) for
the adsorption of Cd(II). Afterward, Fe3 O4 @SiO2 -NH2 was gathered using a permanent
bar magnet. The final Cd(II) concentrations were calculated using an Atomic Absorption
Sustainability 2022, 14, 2290 5 of 21

Spectrometer device (AAS, SL176 Model, Elico Limited, Chennai, India). Cd(II) removal %,
as well as sorption capacity, were calculated with the help of the Equation below:

Co − Ce
 
% Removal = × 100 (1)
Co

Sorption capacity:
(C o − Ce ) V
qe = (2)
m
Co (mg/L) and Ce (mg/L) denote initial and equilibrium concentrations for the
cadmium ion solution, respectively. V denotes the volume of the cadmium ion solution (L),
m denotes the mass of the Fe3 O4 @SiO2 -NH2 nanoparticles (gram).

2.6. Thermodynamic Study

The thermodynamic parameters, for example, the enthalpy change (∆H◦ ), Gibbs free
energy change (∆G◦ ) and standard entropy change (∆S◦ ) were estimated from the following
equations (Equations (3)–(5))
The thermodynamic experiment was conducted by reckoning 0.2 g of Fe3 O4 @SiO2 -
NH2 nanoparticles with a series of conical flasks consisting of 100 mL cadmium ion so-
lution, accompanied by various initial concentrations ranging from 25 to 150 mg/L, and
temperatures ranging 303–333 K. Fe3 O4 @SiO2 -NH2 nanoparticles were eliminated through
solutions utilizing a bar magnet. Final Cd(II) ion concentration was calculated using AAS.

CAe
Kc = (3)
Ce

∆Go = −RTlnKc (4)

∆So ∆Ho
 
CAe
log = − (5)
Ce 2.303 R 2.303 RT
where CAe denotes the amount of cadmium ions attached to the Fe3 O4 @SiO2 -NH2 (mg/L),
Kc denotes equilibrium constant, Ce denotes equilibrium cadmium ion concentration
(mg/L), T denotes temperature (K) and R denotes universal gas constant (8.314 J/mol/K).

2.7. Isotherm Modelling

The Langmuir equation is as follows [26]:

qm KL Ce
qe = (6)
1 + KL Ce

The equilibrium parameter is:

1
RL = (7)
1 + KL Co

The Freundlich isotherm model is presented as follows [27]:

1
qe = KF Cen (8)

Temkin adsorption isotherm model is given below [28]:

qe = B ln (A Ce (9)

where qe (mg/g) denotes adsorption capacity for Cd(II) at equilibrium state, KL is the
sorption Langmuir constant (L/mg), qm denotes maximum cadmium ion adsorption
capacity (mg/g), KF is the Freundlich sorption constant ((mg/g)(L/mg)(1/n) ), n denotes
Sustainability 2022, 14, 2290 6 of 21

the intensity of adsorption constant (g/L), B = RT/b is the heat of adsorption constant,
b denotes heat of adsorption (kJ/mol), A is constant of Temkin isotherm (L/mg).

2.8. Kinetic Modeling

The sorption kinetics confirmation is significant for assessing the efficiency and sys-
tem of the sorption. The kinetics experiments were conducted at various concentrations
(25 to 150 mg/L) with 0.2 g of Fe3 O4 @SiO2 -NH2 nanoparticles at different time periods
(10 to 60 min) on an incubation shaker. The Fe3 O4 @SiO2 -NH2 nanoparticles were separated
by a bar magnet, and using the AAS, the residual amount of Cd(II) was calculated. The
quantity of Cd(II) ions adsorbed onto Fe3 O4 @SiO2 -NH2 nanoparticles at different time
intervals qt (mg/g) was calculated by:

(Co − Ct )
qt = V (10)
m
where Ct denotes concentration of cadmium ions at a given time t (mg/L), qt is the amount
of Cd(II) ion adsorbed/g of adsorbent at any time t.
Collected kinetic data were analyzed by the pseudo-first-order [29], pseudo-second-
order [30] as well as the Elovich kinetic [31] models in explaining sorption processes.
Pseudo-first order kinetic model:

qt = qe [1 − exp(−K1 t)] (11)

Pseudo-second order kinetic model:

q2e k2 t
qt = (12)
1 + qe k2 t

Elovich kinetic model:

qt = (1 + βE ) ln(1 + αE βE t) (13)

where qe and qt are the quantity of adsorbed Cd(II) ions onto Fe3 O4 @SiO2 -NH2 nanoparti-
cles (mg/g) at equilibrium and at a given time, t denotes time (min), k1 denotes pseudo-
first-order sorption constant (min−1 ), k2 denotes pseudo-second-order sorption constant
(g/mg min) as well as k2 ·qe 2 = h denotes initial sorption rate (mg/g min). αE denotes the
initial sorption rate mg/(g min) and βE (g/mg) is the desorption constant.

2.9. Adsorption Mechanism Validation

To describe sorption mechanisms, intraparticle diffusion [32], Boyd kinetic [33] and
shrinking core models [34] were used, as shown below.
Weber and Morris intraparticle diffusion model:

qt = kp t1/2 + C (14)

The Boyd kinetic model:

 
q
− 0.4977 − ln 1 − t = Bt (15)
qe

The effective diffusivity, Di (m2 /s), was calculated by the following equation:

π2 Di
B= (16)
r2

kp denotes the intraparticle diffusion constant (mg/g min0.5 ), r denotes Fe3 O4 @SiO2 -NH2
nanoparticles radius and C denotes boundary layer thickness.
Sustainability 2022, 14, 2290 7 of 21

For film diffusion control:

3D
X= α (17)
δrC
Considering particle diffusion control:

2 6D
F(X) = 1 − 3(1 − X) 3 + 2(1 − X) = α (18)
r2 Co
From the slope of the graph between F(X) vs. α, the diffusivity values are given by:

Co r2
D = (Slope) (19)
6
where:
(C o − C)
X is the extent of reaction =
(20)
(C o − Ceq
Zt
α= C dt (21)
0

Co denotes initial cadmium ions (mg/L), C denotes final cadmium ions (mg/L),
r denotes Fe3 O4 @SiO2 -NH2 nanoparticles (m) radius and Co denotes average cadmium
ions site density of the Fe3 O4 @SiO2 -NH2 nanoparticles (mg/L).

2.10. Reusability/Regeneration Studies

Examining the effective regeneration and possible reuse of adsorbents are two vital
factors in industrial operation. An ideal adsorbent has greater potential for cost reduction,
practical reusability and excellent adsorbent storage ability. Fe3 O4 @SiO2 -NH2 nanoparticles
possess a lower capacity of adsorption at high pH values; acid treatment is a possible
method to achieve effective regeneration of Fe3 O4 @SiO2 -NH2 nanoparticles [35]. Hence, the
sorbent Fe3 O4 @SiO2 -NH2 -adsorbed Cd(II) material was treated with 0.1 M Hydrochloric
acid solution for two hours and cleaned using deionized water till the pH was near 7.
Later, the nano sorbent was dehydrated using vacuum on 323 K. Regenerated sorbent was
utilized for further Cd(II) sorption cycles.

3. Results and Discussion

3.1. Characterization Study
3.1.1. XRD Pattern of Fe3 O4 @SiO2 -NH2 Nanoparticles
Figure 2a exhibits the X-ray diffraction (XRD) pattern of amino-functionalized
Fe3 O4 @SiO2 nanoparticles. The XRD pattern shows intense diffraction patterns at 2θ = 30.56◦ ,
35.88◦ , 43.94◦ , 53.72◦ , 57.33◦ and 62.13◦ , which correspond to the miller indices of the re-
flecting planes for (220), (311), (400), (422), (511) and (440), respectively. These observed
reflections as series go well along with the inverse spinel structure exhibited by Fe3 O4 . The
acquired results are well-matched to standard JCPDS File No. 65–3107 [36,37]. The diffrac-
tion patterns at around 2θ = 20◦ correspond to the amorphous silica shell, which covers
the core Fe3 O4 for strengthening the outer structure [38]. From the previous studies [39], it
was reported that the 3-aminopropyltrimethoxysilane (APTS) functionalized Fe3 O4 @SiO2
nanoparticles exhibit a similar spinel structure with the face centered cubic (FCC). Vari-
ous researchers showed that the (3-aminopropyl)-triethoxysilane (APTES) functionalized
Fe3 O4 @SiO2 nanoparticles exhibit a similar spinel ferrite crystal structure [40,41]. The syn-
thesized amino-functionalized Fe3 O4 @SiO2 nanoparticles show spinel ferrite patterns [42].
Sustainability 2022, 14, 2290 8 of 21

Figure 2. (a) XRD pattern, (b) SEM analysis, (c) EDAX analysis, (d) TEM analysis of amino-
functionalized Fe3 O4 @SiO2 nanoparticles.

3.1.2. Surface Morphology of Fe3 O4 @SiO2 -NH2 Nanoparticles

Figure 2b–d depicts the SEM image, EDAX pattern and TEM image of amino-functiona
lized Fe3 O4 @SiO2 nanoparticles. The prepared nanoparticle morphological changes were
examined utilizing SEM analysis. Meanwhile, peaks corresponding to elements were
studied using the EDAX analysis. The in-depth morphological study (TEM) images sug-
gest that the spherical shape of the particles and the Fe3 O4 was sequentially coated with
SiO2 , which confirms the formation of the core-shell structure of amino-functionalized
Fe3 O4 @SiO2 nanoparticles. After functionalizing through the grafting of APS on the surface
of Fe3 O4 /silica, core-shell particle shape was preserved [43]. The SiO2 layer could provide
the Fe3 O4 nanoparticles with a good acid resistance property [44].

3.1.3. FTIR Analysis of Fe3 O4 @SiO2 -NH2 Nanoparticles

FT-IR spectra were documented in order to characterize the fabrication process and to
validate the modification of Fe3 O4 @SiO2 nanoparticles by the amine group. From Figure 3a,
the absorption band at 538.23 cm−1 corresponds to magnetite’s Fe-O vibration [45], and
the absence of typical carboxyl peaks in the spectrum corresponds to oleic acid stabilized
nanoparticles, obtained by the interaction between carboxyl groups and nanoparticles,
which enhance the structural strength of nanoparticles. The bands at 810.25 cm−1 and
1031.81 cm−1 seemed familiar to symmetric stretching vibration, as well as the deformation
vibrations, which confirm the silica coating on Fe3 O4 nanoparticles [46]. The characteristic
peak at 965.15 cm−1 corresponds to the silanol group (Si-OH), which confirm the amino-
functionalized Fe3 O4 @SiO2 nanoparticles [47]. The absorption peaks at 3286.55 cm−1 ,
1632.46 cm−1 and 695.26 cm−1 were attributed to amino group stretching and bending
Sustainability 2022, 14, 2290 9 of 21

vibration [48]. Absorption peaks at 2919.23 cm−1 correspond to the -CH2 - vibrations
in amino-functionalized Fe3 O4 @SiO2 nanoparticles. This analysis helped to identify the
fabrication of the silica shell as an outer layer on the Fe3 O4 nanoparticles.

Figure 3. (a) FTIR analysis, (b) magnetization curve, (c) TGA analysis of amino-functionalized
Fe3 O4 @SiO2 nanoparticles.

3.1.4. Magnetism and Dispersibility Nature of Fe3 O4 @SiO2 -NH2 Nanoparticles

The magnetization curve of the amino-functionalized Fe3 O4 @SiO2 -NH2 nanoparticle
(VSM) results is shown in Figure 3b. Magnetic properties exhibited by the synthesized
nanoparticles were represented by utilizing a magnetization curve. It was observed that
the amino-functionalized Fe3 O4 @SiO2 -NH2 nanoparticles exhibited a superparamagnetic
nature [49]. The reductions in the saturation value mainly correspond to the isolation
effect of the outer layer of silica [50]. Thus, the obtained amino-functionalized Fe3 O4 @SiO2 -
NH2 nanoparticles led to the simultaneous decrease of coercivity [51]. Immediately after
applying the magnet, the gathering of magnetic particles took place, as shown in Figure 3b.

3.1.5. Thermogravimetric and DSC Analysis of Fe3 O4 @SiO2 -NH2 Nanoparticles

Thermogravimetric analysis (TGA) is a method of thermal study where variations in
chemical as well as physical properties in materials are studied with the dependence of
a constant rise of temperature or, as a function of time, having non-varying temperature
and mass loss. TGA gives data on physical phenomena, like the second-order phase
transitions, sublimation, vaporization, adsorption, desorption and absorption [49]. Thermo-
gravimetric analysis (TGA), as well as differential scanning calorimetry (DSC) analysis,
were mainly performed for investigation of the thermal characteristics of the prepared
samples. Figure 3c shows the TGA-DSC curves of amino-functionalized Fe3 O4 @SiO2 -NH2
nanoparticles. The prepared nanoparticles show an exothermic peak from the DSC pattern
at around 503 K, 603 K, 773 K and 953 K, respectively [52]. From the TGA pattern, the
first weight loss was noticed between 373 K as well as 573 K, attributed to evaporation by
water molecules that were adsorbed [53]. Second weight loss was noticed between 573 K
and 773 K due to the dehydration of hydroxyl groups and decomposition of the remaining
organic constituent [54]. The final weight loss took place > 773 K.
Sustainability 2022, 14, 2290 10 of 21

3.2. Batch Adsorption Study

3.2.1. Impact of pH on Adsorption and Point of Zero Charge (pHpzc )
The pH of the cadmium ion solution is the vital parameter to be considered in the
case of cadmium ion sorption onto Fe3 O4 @SiO2 -NH2 nanoparticles. The adsorption test
was conducted in the Erlenmeyer flasks in a series with pH values ranging from 2 to
8. The pH of solution varied with the addition of 0.01 M hydrochloric acid, as well as
sodium hydroxide. Sorption temperature (303 K) and the interaction time (30 min) were
kept to achieve the adsorption equilibrium [55]. The adsorbents were recovered from the
medium using a magnet. The supernatant was subjected to AAS for analyzing the residual
concentration of Cd(II). The pH effect on the sorption method is depicted in Figure 4a.
If the pH is low, the removal percentage and qe were found to be low; this is due to the
increase in the number of hydronium ions (H+ ) present in the medium. The amino groups
on Fe3 O4 @SiO2 -NH2 are prone to protonation and deprotonation [56].

MNP − S − NH2 + H+ = MNP − S − NH3+ (22)

MNP − S − NH2 + Cd(II) = MNP − S − NH2 Cd(II) (23)

The protonation and deprotonation steps related to MNP-S-NH2 in the medium are
depicted by Equation (22). At the same time, Equation (23) shows the complex product
formation that occurs with the help of Cd(II) ions using amino groups, appearing in the
outer layer of MNP-S-NH2 .
Uptake capacity seen for the pH 7.0–9.0 range tends to be reduced because of the
formation of (Cd(OH)+ ) species. However, if the pH of the sorbate solution turns out to
be greater than pHpzc (point of zero charge), the anions on the sorbent layer tend to be
increased with the cation adsorption capacity. The point of zero charge of the Fe3 O4 @SiO2 -
NH2 sorbent was found to be greater than 6.0, which resulted in cadmium ion precipitation
as Cd(OH)+ ). Therefore, pH 6.0 was a substantial pH for the Fe3 O4 @SiO2 -NH2 -cadmium
adsorption system.

3.2.2. Impact of Dosage on Adsorption

The achieved optimum condition for the amount of Fe3 O4 @SiO2 -NH2 adsorbent in
removing metal ions is shown in Figure 4b. The amount of Fe3 O4 @SiO2 -NH2 nanoparticles
is pivotal to maximizing the adsorption efficiency. In this research, a freshly prepared
Fe3 O4 @SiO2 -NH2 range, starting with 0.5 g/L till 3 g/L with a Cd(II) concentration of
50 mg/L, was carried out. The information noted through experiments is represented in
Figure 4b. As there was a rise in the sorbent dosage of Fe3 O4 @SiO2 -NH2 nanoparticles, the
percentage of removal increased, but the qe decreased. From this trend, it can be clearly
understood that a rise in the number of active sites favors sorption [57]. From the results
depicted in Figure 4b, it was observed that 2.0 g/L seems to give ample interchangeable
binding sites for the removal of cadmium ions. Beyond this, the removal of cadmium ions
was not changed appreciably. Therefore, in the following experiments, the sorbent dosage
of Fe3 O4 @SiO2 -NH2 nanoparticles was fixed at 2 g/L.

3.2.3. Impact of the Amount of Cadmium Ions

Adsorption of Cd(II) onto Fe3 O4 @SiO2 -NH2 nanoparticles was also performed with
different initial Cd(II) ion concentrations (25 mg/L till 150 mg/L) (Figure 4c). Figure 4c
shows that equilibrium adsorption capacity qe rose when the initial cadmium ion concen-
tration increased. However, the removal % was reduced. qe values were raised, starting
with 12.473 till 65.686 mg/g, whereas removal % reduced in the order of 99.785 to 87.582%,
corresponding to initial cadmium ion concentrations ranging from 25 mg/L to 150 mg/L.
Lower metal ion concentrations give a vital push force for the competing mass transfer
resistances [58]. This adsorption behavior showed the surface saturation to be relying upon
the initial cadmium ion concentration. The ratio of surface-active sites to the cadmium
ions in the medium may be more for lower cadmium ion concentrations. Hence, all the
Sustainability 2022, 14, 2290 11 of 21

cadmium ions may influence the Fe3 O4 @SiO2 -NH2 sorbent, and the cadmium ions were
expelled from the aqueous medium.

Figure 4. Impact of factor-influencing parameters for the removal of Cd(II) onto Fe3 O4 @SiO2 -
NH2 nanoparticles. (a) pH, (b) adsorbent dose, (c) Cd(II) ion concentration, (d) interaction time,
(e) temperature, (f) thermodynamic study.

3.2.4. Impact of Interaction Time

Figure 4d exhibits the influence of interaction time seen on Cd(II) ion adsorption.
Figure 4d found that removal efficiency, as well as equilibrium adsorption capacity, in-
creased rapidly and then reached a saturated state (approximately 30 min). Nevertheless,
increasing the contact time did not show any drastic changes in percentage removal. It was
observed that the removal percentage and qe values were higher, which resulted from the
Sustainability 2022, 14, 2290 12 of 21

high availability of binding sites in the layer of Fe3 O4 @SiO2 -NH2 nanoparticles. Therefore,
the contact time of 30 min was chosen to be the desired value in the following experiments.
However, at a later stage, the rate of removal was minimum, as determined by the
intraparticle diffusion of the Fe3 O4 @SiO2 -NH2 nanoparticles. It was clearly evident that
the double stage of the adsorption mechanism took place. The first stage was quantitatively
predominant, and the second stage was insignificant.

3.2.5. Impact of Temperature

Temperature has a prominent influence on metal removal by sorption. Similarly, the
influence of temperature on the sorption mechanism of cadmium ions by Fe3 O4 @SiO2 -NH2
nanoparticles was studied in the range of 303 K–333 K and values are portrayed in Figure 4e.
Figure 4e shows that the percentage removal lowers with rising temperature. These
observations conclude that the cadmium ion adsorption by Fe3 O4 @SiO2 -NH2 nanoparticles
was exothermic. At high temperatures, the molecules in the excited state weaken the bonds
between the cadmium ions and the active site for the sorbent. This may be the reason for the
negative correlation between cadmium ions and temperature. The maximum adsorption
was experienced at 303 K for the Fe3 O4 @SiO2 -NH2 -cadmium system.

3.2.6. Thermodynamic Study

The thermodynamic parameters for the Fe3 O4 @SiO2 -NH2 nanoparticle-cadmium
system were calculated from log Kc vs. 1/T plots (Figure 4f), and the findings are listed in
Table 1. From Table 1, the negative values of ∆Ho confirm that the adsorption procedure
leads to the heat releasing condition, which corresponds to the exothermic nature of the
Fe3 O4 @SiO2 -NH2 nanoparticle-cadmium system. This is possible due to the temperature
increase; the cadmium ions move firstly to the previous layer, which creates a tendency of
desorbing cadmium ions from the Fe3 O4 @SiO2 -NH2 nanoparticle surface.

Table 1. Thermodynamic parameter study for the adsorption of Cd(II) ion onto Fe3 O4 @SiO2 -NH2
nanoparticles.

Concentration of ∆Ho ∆So ∆Go (kJ/mol)

Cd(II) ion (mg/L) (kJ/mol) (J/mol K) 303 K 313 K 323 K 333 K
25 −134.17 −390.90 −15.467 −9.630 −8.664 −7.810
50 −30.912 −69.115 −8.999 −7.935 −7.320 −6.529
75 −18.631 −35.907 −6.995 −6.682 −6.048 −5.548
100 −9.780 −12.654 −5.948 −5.752 −5.018 −4.755
150 −10.011 −16.159 −4.920 −4.647 −4.296 −3.941

3.3. Modeling Study

3.3.1. Adsorption Isotherm Study
Depicted by Figure 4 and Table 2, the Freundlich adsorption isotherm model can well
be portrayed by the adsorption equilibrium data. Additionally, it fits more, along with
the isotherm data, having high R2 in comparison to the Langmuir and Temkin models.
This pointed out that nonideal adsorption occurred with a heterogeneous surface of the
Fe3 O4 @SiO2 -NH2 nanoparticle adsorbent, as well as multilayer cadmium adsorption [56].
The Langmuir maximum monolayer adsorption capacity (qmax ) of the Fe3 O4 @SiO2 -NH2
for cadmium ions was calculated to be 40.02 mg/g.
Sustainability 2022, 14, 2290 13 of 21

Table 2. Adsorption isotherm parameters for the adsorption of Cd(II) ion onto Fe3 O4 @SiO2 -NH2
nanoparticles.

Adsorption Isotherm Model Parameters Values R2

qm (mg/g) 40.02
KL (L/mg) 0.834
Langmuir 0.8832
SSE 109.2
RMSE 5.97
KF ((mg/g)(L/mg)(1/n) )) 19.67
n (g/L) 3.091
Freundlich 0.9451
SSE 23.56
RMSE 2.987
A 112
B 1.175
Temkin b (kJ/mol) 1.234 0.8045
SSE 117.2
RMSE 5.393

Error functions, such as the root mean square error (RMSE), Chi-square and R2 error,
were calculated for the optimization of process parameters. The smallest value of the error
functions was taken as the best fit model.
n
r
1
∑


RSME = qe − predictedqe (24)
n − 1 i=1

n (qe − Predicted qe )2
Chi Square = χ2 = ∑ Predicted qe
(25)
i=1

SSR Sum of Squares Regression

R2 Error = = (26)
SST Sum of Squares Total
In these equations, n represent the number of observations. In order to identify the
best-fit adsorption model, non-linear models were considered [59]. Although the degree of
determination values were close to 0.85 (Table 2) in isotherm models, the error functions
for the three models varied considerably.
Table 3 depicts the maximum qm of Fe3 O4 @SiO2 -NH2 nanoparticles as indicated by a
higher potential towards other magnetic adsorbents. This might be due to the formation of
adsorption sites for cadmium onto the polymer matrix through adding silica and amino
groups. Furthermore, the magnetic nano sorbents displayed a stable qm of cadmium
after reuse. Due to these outcomes, Fe3 O4 @SiO2 -NH2 nanoparticles are required to be a
predominant attractive magnetic nano sorbent for cadmium removal and recovery from
aqueous solutions. Above this, taking into account the easy synthesis, reusability as
well as separation of MNPs, the Fe3 O4 @SiO2 -NH2 nanoparticles were better adsorbents
than others.

Table 3. Comparison of Cd(II) ion adsorption capacities of Fe3 O4 @SiO2 -NH2 nanoparticles on
different adsorbents.

Adsorbents qm (mg/g) References

Magnetic chitosan 48 [58]
Fe3 O4 @SiO2 -NH2 nanoparticles 40.02 This work
Amino-functionalized MNPs 40.10 [59]
Magnetic nanoadsorbents 36.00 [53]
HA-Fe-PILC 31.34 [54]
Sustainability 2022, 14, 2290 14 of 21

Table 3. Cont.

Adsorbents qm (mg/g) References

Magnetic composites-carbon nanotubes 31.25 [55]
Iron oxide coated sewage sludge 42.40 [56]
Manganese oxide-carbon nanotube 26.24 [57]
Sugar beet pulp 24.3 [58]
Fe3 O4 @APS@AA-co-CA MNPs 29.6 [59]
oxMWCNT6h 13.5 [60]
Granular sludge-clay 1.53 [61]

3.3.2. Adsorption Kinetics and Mechanism

Figure 5 showed the adsorption kinetics for Cd(II) ions by Fe3 O4 @SiO2 -NH2 nanopar-
ticles at 303 K. For ensuring the enhanced interpretation of the adsorption kinetic behavior
of Cd(II) ions on the Fe3 O4 @SiO2 -NH2 nanoparticles, the most typical kinetic models like
the pseudo-first, pseudo-second and intraparticle diffusion model, Elovich model, SCM
model and Boyd Kinetic model have been well established to elucidate relationships of
adsorption rate as well as the adsorption capacities [62]. Results on sorption kinetics for
Fe3 O4 @SiO2 -NH2 nanoparticle Cd(II) removal are portrayed in Figure 5. Table 4 depicts
calculated values of kinetic models and coefficients of determination (R2 ) values. The
calculated equilibrium adsorption capacity (qe ) value of the pseudo-first-order did not
differ much in comparison to the experimental adsorption capacity (qe, (exp)) value. R2
values were found as: pseudo-first-order > pseudo-second-order > Elovich kinetic models.
The chemical adsorption principles can be well portrayed by the Elovich model, which
explains that the adsorbent possesses a heterogeneous surface [63,64]. Hence, from these
findings, it was validated that the pseudo-first-order model is the best apt model to exhibit
the Cd(II) ion eradication by Fe3 O4 @SiO2 -NH2 nanoparticles.

Table 4. Adsorption kinetic parameters for the adsorption of Cd(II) ions onto Fe3 O4 @SiO2 -NH2
nanoparticles.

Kinetic Concentration of Cadmium Ion Solution (mg/L)

Parameters
Model 25 mg/L 50 mg/L 75 mg/L 100 mg/L 150 mg/L
qe, exp (mg/g) 12.4899 25.4677 35.4566 45.99 65.956

Pseudo-first- k1 (min−1 ) 0.0943 0.08508 0.08162 0.07375 0.06614

order qe, cal (mg/g) 12.8 25.13 36.63 47.96 69.89
equation
R2 0.9636 0.9739 0.9663 0.9596 0.9396

Pseudo- k2 (g mg−1 min−1 ) 0.008046 0.003395 0.002143 0.00135 0.0007472

second-order qe ,cal (mg/g) 14.93 29.88 43.96 58.87 88.2
equation
R2 0.8858 0.9146 0.9059 0.9064 0.8894
α (mg/g.min) 8.215 0.6823 0.3036 0.125 0.04648
Elovich kinetic
β (g/mg) 0.227 1.677 3.087 4.927 8.666
model
R2 0.7977 0.8445 0.8374 0.8477 0.8374
Sustainability 2022, 14, 2290 15 of 21

Figure 5. Adsorption kinetic study for the removal of Cd(II) onto Fe3 O4 @SiO2 -NH2 nanoparticles.

In the solid-liquid sorption technique, the exchange of solutes can be either an external
mass transfer, an intraparticle diffusion or a combined method [65,66]. In the case of the
removal process under study, Cd(II) is transported through the following sequences below:
1. Film-type diffusion, where ion transfer from the bulk portion through the liquid film
to the adsorbent surface;
2. Intraparticle diffusion characterized by moving through adsorbent pores;
3. Adsorption, the ions may be attached to the active sites of the adsorbent.
Sustainability 2022, 14, 2290 16 of 21

Even though the intraparticle diffusion model was evaluated more, to convey the
adsorption mechanism, it should be analyzed for different metal ion concentrations. With
regard to the graph of qt vs. t1/2 , the first step represents a rapid transfer of Cd(II) ions from
the bulk solution to the Fe3 O4 @SiO2 -NH2 nanoparticle surface. The second step represents
the slow diffusion of Cd(II) ions from the external surface into the intra-particle, marking it
as the rate-determiner. The slope was defined as the intraparticle diffusion rate constant
kp . Furthermore, a larger intercept represents the surface sorption’s huge contribution.
The final step illustrates the equilibrium adsorption of Cd(II) ions in the inner surfaces of
Fe3 O4 @SiO2 -NH2 nanoparticles. Values of kp and C were calculated from the slope as well
as the intercept, respectively, of qt versus t1/2 represented in Figure 6a. From the slope of
the linear portion of the plot, the intraparticle adsorption parameter kp was found to be
1.013, 2.212, 3.359, 4.815, and 7.694 mg/g.min1/2 . The boundary layer effect was explained
by the surface sorption factor C (mg/g) featured by the intercept of the diffusion plot.
In this study, the C factor was found to increase for the initial Cd(II) ion concentrations
(Table 5) [67]. The slowest step in the sorption of cadmium ions by Fe3 O4 @SiO2 -NH2
nanoparticles was given by the Boyd kinetic model. The adsorption kinetic data fit well
with the Boyd kinetic model, and the results are shown in Figure 6b. The graphs were
found to be a straight line; however, they did not pass the origin [68].

Figure 6. Adsorption mechanism for the removal of Cd(II) onto Fe3 O4 @SiO2 -NH2 nanoparticles.
(a) Weber and Morris intraparticle diffusion, (b) Boyd kinetic, (c) Particle diffusion control.

The effective diffusion coefficient (Di ) data was computed with Equation (16), and
the data are presented in Table 5. Figure 4c represents the shrinking core model, which
influences the particle diffusion on the current adsorption system was scrutinized. From
these findings, it was also clearly seen that particle diffusion might make changes in the
present adsorption system. Diffusivity (D) values were computed utilizing Equation (19),
and values are presented in Table 5. Taking the above results from kinetic models into
consideration, both film as well as particle diffusion, could be involved in the adsorption of
cadmium ions onto the Fe3 O4 @SiO2 -NH2 nanoparticles.
Sustainability 2022, 14, 2290 17 of 21

Table 5. Adsorption mechanism parameters for the adsorption of Cd(II) ions onto Fe3 O4 @SiO2 -NH2
nanoparticles.

Adsorption Concentration of Cadmium Ion Solution (mg/L)

Parameters
Models 25 50 75 100 150
kp (mg/g min1/2 ) 1.013 2.212 3.359 4.815 7.694
Intraparticle
diffusion C (mg/g) 5.636 9.364 12.58 13.11 13.50
model
R2 0.670 0.748 0.741 0.759 0.754
B 0.101 0.109 0.118 0.125 0.132
Boyd kinetic
Di (×10−12 m2 /s) 5.343 5.766 6.242 6.612 6.983
model
R2 0.760 0.883 0.862 0.857 0.867
D (×10−9 m2 /s) 3.2564 3.1829 3.0978 3.0124 2.7893
SCM model
R2 0.751 0.747 0.798 0.747 0.734

3.4. Desorption and Reuse of Fe3 O4 @SiO2 -NH2 Nanoparticles

Figure 7a showcases the desorption kinetics for Cd(II) desorption from Fe3 O4 @SiO2 -
NH2 nanoparticles. Therefore, the desorption of Fe3 O4 @SiO2 -NH2 molecules can be
completed by washing with a high concentration of HCl solution [69]. The adsorp-
tion/desorption cycles were continuously carried out nearly five times. Figure 7b depicts
that the sorption capacity of Cd(II) ions by Fe3 O4 @SiO2 -NH2 nanoparticles underwent a
reduction from 95 to 80% at the end of five consecutive cycles. Hence, the experimental
outcomes confirmed that Fe3 O4 @SiO2 -NH2 nanoparticles could be reusable and also an
efficient sorbent for the successful eradication of removing Cd(II) ions.

Figure 7. (a) Desorption kinetic plot. (b) Regeneration studies for the removal of Cd(II) ions onto
Fe3 O4 @SiO2 -NH2 .

4. Conclusions
In this experimental study, economically feasible amino-functionalized Fe3 O4 @SiO2 -
NH2 novel magnetic nano sorbent was prepared by co-precipitation via the silica coating
and amine functionalization. Characterization like FT-IR, TEM, SEM and EDX analysis,
XRD, VSM and TGA-DSC analyses were performed to validate the magnetic nano sorbent’s
structure, surface morphology and potential elements. FT-IR and XRD analysis concluded
that the Fe3 O4 @SiO2 -NH2 nanoparticles have possible functional moieties amorphous in
nature. VSM and TGA-DSC studies were performed to validate the magnetic properties
and thermal stability of the Fe3 O4 @SiO2 -NH2 nanoparticles. Meanwhile, the optimized
values on various process parameters were demonstrated: the initial Cd(II) ion concen-
tration of 50 mg/L, pH 6.0, Fe3 O4 @SiO2 -NH2 dosage 2.0 g/L, the temperature 303 K and
the contact time 30 min for maximum removal of Cd(II) ions. The batch sorption stud-
ies prove that the pseudo-first-order kinetics and the Freundlich isotherm models were
Sustainability 2022, 14, 2290 18 of 21

well fitted to the experimental data. The maximum adsorption capacity was found to be
40.02 mg/g. Moreover, the thermodynamic study revealed that the Cd(II) ion removal by
Fe3 O4 @SiO2 -NH2 nanoparticles was viable, exothermic in nature and spontaneous. Fur-
thermore, the acid treatment could easily regenerate the Fe3 O4 @SiO2 -NH2 nanoparticles,
and the sorption property remained unchanged after the completion of five cycles. There-
fore, amino-functionalized silica magnetic nano sorbent is one of the efficient adsorbents in
removing Cd(II) ions from an aqueous solution. Subsequently, we expect these findings to
give a new understanding of the eco-friendly techniques and tailoring of novel adsorbents.

Author Contributions: Data curation, S.I., S.S., J.A.K. and K.V.A. Formal analysis, S.I., S.S., J.A.K.
and K.V.A. Investigation, D.P. and P.S.K.; Methodology, D.P. and P.S.K.; Resources, S.I., S.S., J.A.K.
and K.V.A.; Supervision, P.S.K.; validation, P.S.K.; writing—original draft, D.P. All authors have read
and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available upon request from the
corresponding author.
Acknowledgments: We are grateful to the management of the Sathyabama Institute of Science and
Technology for providing the research facilities that greatly assisted in this work.
Conflicts of Interest: The authors declare no conflict of interest.

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