Chemical Engineering Journal Advances 8 (2021) 100193

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Chemical Engineering Journal Advances

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Green synthesis of magnetic nanocomposite by Cordia Africana (CA)

leave extract for the treatment of Methylene blue contaminated water
Abenezer Zenebe b, 1, Kabir-ud-Din b, *, Ali Mohammed Yimer b, Sabu Kuzhunellil b,
Hailu Demissie a, 1, *
a
Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
b
Department of Chemistry, College of Natural Sciences, Arba Minch University, Arba Minch, Ethiopia

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

Keywords: The magnetic behavior of individual magnetite (Fe3O4) nanoparticles (MNPs) has arisen considerable attention
Magnetite NPs in environmental application. However, magnetic properties and stability weaken due to their high susceptibility
Natural natrolite to chemical activity (oxidation). Efforts have increasingly been made to encapsulate MNPs by green organic
Adsorption
matrix, which considerably improve functionality, stability, cost and reduce back toxicity. Besides, the use of
Methylene blue
natural zeolite materials has been reported to endows considerable dispersibility and chemical stability for the
Response surface methodology (RSM)
composite MNPs. In this study, bio-based magnetite nanoparticles were synthesized using an aqueous extract of
Cordia Africana (CA) leaves incorporated into the modified Natrolite (NAT) framework as an adsorbent for
methylene blue (MB)dye removal from aqua solution. The prepared high dispersible Magnetite-NAT Nano­
composite (M/NAT-NC) was characterized by Fourier transform infrared spectroscopy (FTIR), powder X-ray
diffraction (XRD), and scanning electron microscope (SEM). The optimum adsorption efficiency of M/NAT-NCs
was estimated by employing Response Surface Methodology (RSM)-based Box-Behnken Design (BBD) at different
parameters. Accordingly, 0.5 g M/NAT-NCs, 40 mg/L, and pH 9 at 40 min were found to be the optimal con­
ditions for best removal (98.6%). The adsorption data fitted best with the pseudo-second-order and Freundlich
model, and the negative value of ∆G0 confirms the feasibility and spontaneity of the MB adsorption onto M/NAT-
NCs. Besides, the regeneration of exhausted M/NAT-NCs reflected nearly similar removal efficiency as the new
one; as such, M/NAT-NCs could be reasonably used for cationic dyes removal from aqueous media.

Introduction their recent increasing application in silk, textile cosmetics, leather,

Much has been said about the impact of industrialization and
consequently their byproducts emission on environmental deterioration.
Nowadays, a roughly estimated production of 106 tons per year of about
100,000 commercial dyes has been reported, of which over 15% of such
huge annual production and 1–10% loss during their application process
disposed to the environment and potentially disturbing aquatic organ­
isms [1–3]. Notably, the presence of toxic organic dyes like methylene
blue (MB) in outlet water, even at trace concentration, is considerably
perilous due to blockage of solar photons radiating to marine systems,
and consequently inhibition effect on photosynthetic and other biolog­
ical processes in the aquatic environment [4]. Therefore, the removal of
dyes (MB) from contaminated water to a risk-free level is a hot topic in
light of improper discharge of dye waste to the water bodies as well as
food, pharmaceutical, and paper industries [5,6].
Among various methods which have been employed for dye cleaning
from water, generally, separation methods could be considered a
promising approach than destruction as the target molecules can be
recollected depending on their cost and importance at the end of the
process [7]. Among solute separation methods [8,9], adsorption is more
economical and more eco-friendly due to its design simplicity, wide
adaptability to the versatile system, suitability, ease of operation, and
has wide potential applications in the various system [10–13]. The
process efficiency depends on the nature of the materials used. Recently,
numerous adsorbent materials have been used as an adsorbent, such as
polymers [14–16], clays/zeolites [17–19], activated carbons (ACs) [20,
21], Fe3O4 nanoparticles [12,22], and other porous materials [3,23–27].
Particularly activated carbon is commonly utilized to sorb organic

* Corresponding authors.
E-mail addresses: kabirarba@gmail.com (Kabir-ud-Din), mayetebise@gmail.com (H. Demissie).
1
Contributed equally

https://doi.org/10.1016/j.ceja.2021.100193
Received 30 July 2021; Received in revised form 28 September 2021; Accepted 13 October 2021
Available online 16 October 2021
2666-8211/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A. Zenebe et al.
Scheme 1. Route of M/NAT-NCs synthesis.
compounds since it has a porous structure and active sites with a large
specific surface[5]. However, its application is negated by the high cost
of best quality AC and the difficulty as well as the cost of adsorbent
recovery through several step processes [28]. Consequently, searching
for alternative efficient, simple, and low-cost adsorbent materials like
zeolites has been known to be a common practice.
Zeolites are well-known hydrated alumino-silicate minerals that can
be obtained either from naturally occurring deposits or manufactured
synthetically and are highly recognized as low-cost adsorbents due to
their abundant availability [29,30]. They are also known by interesting
features such as high surface area, micro-pores structure, a variety of
channels, and high resistance towards chemical and heat fluctuation
[31,32]. Among zeolites, the natrolite (NAT) is a common portion of the
zeolite group and is known by its needle-like crystal propensities. It is a
fibrous zeolite with small pores and Al2Si3O10 main structural unit,
which generally comprises eight members of oxygen ring systems (pore
diameter <4.5 Å), and the Na+cations occupying the positions in the
eight-ring channels [31,33]. Natrolite zeolite possesses a net negative
charge, which enables the adsorption of basic dyes. Besides, the ease of
its regeneration, often through filtration, makes it a cost-effective ma­
terial, although post-treatment remains a challenge in practical appli­
cations. However, incorporating magnetically driven adsorbents would
efficiently enhance separation (sedimentation) of the bound solute and
sorbent matrix by utilizing an applied magnetic field, which signifi­
cantly reduces energy consumption and prevents the loss of adsorbent
during centrifugation or filtration [15,34].
Since a few years back, iron oxide nanoparticles (NPs) such as
maghemite (γ-Fe2O3) nanoparticles (MhNPs), magnetite (Fe3O4) nano­
particles (MNPs), etc. have been extensively investigated due to abun­
dance, cheapness, non-toxicity, quick response, high surface area to
volume ratio and high removal efficiency of organic compounds. The
utilization of MNPs as an adsorbent in water treatment gives an
appropriate and comfortable approach for isolating and removing pol­
lutants by applying external magnetic fields [35]. However, MNPs have
a limited capacity for large molecules accommodation due to their small
pores and prolonged diffusion process [8]. Besides, the high suscepti­
bility to chemical activity, particularly for oxidation, leads to weakening
the magnetic properties of MNPs [22]. The regulation of MNPs particle
size during synthesis has always been the main challenge in their
application as the particles are suspectable for agglomeration in order to
decline their surface energy. Therefore, the synthesis of core-shell type
surface-functionalized MNPs has attracted much attention because the
polymer shell prevents the agglomeration of the core MNPs to a very
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Chemical Engineering Journal Advances 8 (2021) 100193
large size and improves their stability [15,22]. The use of bio extracts as
a polymer matrix makes the nanocomposite products more efficient and
eco-friendlier. For example, Cordia Africana leaf extract, CA (Wanza,
Lam), has both basic and acids functional groups for effective removal
for cationic dyes as well as anionic dyes; also, it is easily accessible in
different tropical zones of Ethiopia (wild and ornamental plant).
Meanwhile, impregnation/coating of the MNPs into/onto microporous
aluminosilicates NAT may be a promising alternative to enhance
adsorption efficiency, dispersion stability in a suspension medium,
structural diversity, thermal stability, and recovery [36,37]. Thus, syn­
thesizing biofunctionalized and colloidal porous materials with high
dispersibility, adsorption/hydrophobicity, magnetically driven rapid
separation capacity, and ease of recovery is a promising technique for
aqua remediation.
In the present study, we report an eco-compatible and simple
approach for the synthesis of MNPs using CA as a sorbent for MB dye.
Where the CA was expected to convert ferro ions into nanoparticles
(without their agglomeration) and endows functionality. Besides, NAT
was injected into the synthesis media to enhance the adsorption capacity
and thermal stability of the resulting material. However, NAT base
treatment was conducted because hydroxide ions (OH–) are amenable to
bind with functional groups, even including hydroxyl groups, which
induce negative charges on the NAT functional groups. The negative
groups repeal each other, by turn, would enable the exposure of other
functional groups and improve interaction (covalently) with the func­
tionalized nanomaterial as well as the pollutant. The surface
morphology, structure, and adsorption property of NAT, MNPs, and
Magnetite-NAT nanocomposite (M/NAT-NC) were characterized using
UV-Visible spectrometry (UV–Vis), X-ray diffraction (XRD), Scanning
electron microscopy (SEM), and Fourier transform-infrared (FT-IR)
spectrometer. The adsorption capacity of M/NAT-NC for the MB
removal from synthetic water was investigated at various conditions
(adsorbent/adsorbate dosage, pH, and contact time). The Box-Behnken
design (BBD) experimental design approach was used to find the opti­
mum parameters for the adsorption process. Besides, the adsorption
kinetics, thermodynamics, and isotherm models were applied to eval­
uate the adsorption phenomenon.
Materials and methods
Materials
The following analytical grade reagents and chemicals were used
A. Zenebe et al.
without any refinement. NAT (FeCl3•6H2O) (Sigma Aldrich), FeS­
O4•7H2O (Sigma Aldrich), NaNO3 (BDH, England), NaOH (Sigma
Aldrich), HCl (Sigma Aldrich), MB, C16H18N3SCl (Merck, Germany).
Ultra-pure (Milli-Q water) was used for the preparation of MB synthetic
solutions, as a blank, for dilution of samples, and for other purification
purposes. A 5% HCl solution was used to sonicate all the glassware,
followed by repeated rinsing by Milli-Q water.
Synthesis of magnetite nanoparticles
MNPs were synthesized using a simple co-precipitation method.
Briefly, the first approximately 2:1 Fe3+/Fe2+molar solution was pre­
pared by taking 4.72 g of FeCl3•6H2O and 2.78 g of FeSO4•7H2O in 250
mL water followed by mild stirring using a magnetic stirrer for 5 min to
get a homogeneous solution[36]. Afterward, 25 mL of an aqueous CA
extract was added slowly and, after 5 min, freshly prepared 25% NH3
aqueous solution was added drop-by-drop into the reaction mixture
(with burette rate of 3 ml/min) under vigorous stirring to allow
magnetite precipitation (black precipitate) (Scheme 1). While adding
ammonia, the pH was carefully monitored below 10. The resulting
mixture was heated up to 60 ◦ C under atmospheric pressure for 30 min,
cooled to room temperature, and then poured into a beaker. Magnetic
decantation was carried out in order to remove any unwanted particles.
The deposited particles were repeatedly washed with Milli-Q water in
order to remove any residual salts. This solution was subjected to
centrifuge at 5000 rpm for 10 min, oven-dried overnight at 70 ◦ C, and
ground using mortar to break up aggregates and to obtain the powder.
The powder was designated as CAMNPs and used to prepare M/NAT-NC
[38,39].
Base modification of NAT
The raw NAT zeolite sample after oven-dried (105 ◦ C) for 3 h was
milled and sieved into 50 μm. To increase the adsorption capacity of
natural zeolite, the NAT (50 μm) underwent base treatment (beneficia­
tion) as it would limit ion exchange and enhance covalency between the
NAT and magnetic nanomaterial functional groups. Briefly, the sieved
NAT was mixed with 0.1 M NaOH in the ratio of 1:10 (g NAT: mL so­
lution). A magnetic stirrer was used to mix the sample mixture solution
for 2 h. Then, the beneficiation was terminated by adding a large
amount of ultrapure water. Afterward, it was filtered and washed
repeatedly with Milli-Q water until neutral pH was obtained. The filter
cake was left to dry at 105 ◦ C for 12 h before being stored in a desiccator.
Preparation of magnetic nanocomposites (M/NAT-NCs)
The M/NAT-NC was synthesized by impregnation of MNPs onto
beneficiated NAT. Briefly, 4 g of the NAT was added to 2 g of CAMNPs
dispersion in Milli-Q water (100 mL) and continuously stirred at 60 ◦ C
for 90 min. The content was then left for 24 h. Following, the mixture
was washed with ultrapure water and centrifuged to separate the
zeolite/magnetite composite from the solution. It was then overnight
dried at 105 ◦ C. This procedure was utilized by altering temperature, the
stirring time of mixing the two solids, and the proportion of CAMNPs:
NAT [37].
Characterization
The UV-Visible spectrometer (SCOROD-50, Germany) was used to
record absorption spectra. Perkin Elmer, spectrum 65 Spectrometer was
used to recording the FT-IR spectra, in which powder samples were
placed and pressed into thin transparent pellets by thoroughly mixing
with KBr. The XRD patterns were obtained from D8Advanced BRUKER
AXS GmbH, Germany, for average crystallite size and structural deter­
mination of adsorbents. It was conducted at 0.02◦ /s scan rate using Cukα
radiation (1.5406 A0, 45 kV, 40 mA). SEM (JEOL-JSM6610 LV) was
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Chemical Engineering Journal Advances 8 (2021) 100193
employed to examine the morphologies of the samples.
Point of zero charges (pHPZC)
The point of zero charges of the M/NAT-NC was determined using
the salt addition method. Briefly, 0.3 g of M/NAT-NC was added into
50.0 mL of NaNO3 solution (0.1 mol L − 1). The pH was adjusted using a
pH meter to 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 with 0.1 M HCl and 0.1 mol L
− 1
NaOH as needed in each beaker. The mixture was then intermittently
shaken for 24 h to equilibrate the solution. Then, the final pH of each
supernatant was measured carefully after quiescent settling of the
shaken content. The plot of ΔpH (the final pH subtracted from the initial
pH) values versus the initial pH values was obtained to interoperate the
phenomena [19,21]. In which pHPZC was the pH value corresponding to
the ΔpH equals zero. Each set of experiments was conducted in tripli­
cate, and the mean value was recorded.
Dye adsorption study
MB was selected as the model aqua pollutants dye because of the
above-mentioned environmental impacts. The experiments were run in
different Erlenmeyer flasks of 250 mL capacity, each containing 100 mL
of the test solution. The designed solution pH was pre-adjusted using 0.1
M NaOH or HCl. The maximum adsorption efficiency of the M/NAT-NC
was evaluated by optimizing the desired contact time, initial dye con­
centration, temperature, pH, and adsorbent dosage in the batch MB
sorption process. The kinetics of adsorption was studied by taking
samples from the equilibrium mixtures in Erlenmeyer flasks at various
time intervals. An external magnet was used to collect the adsorbents at
different time intervals. The supernatant dye concentration was deter­
mined using UV–Vis spectrophotometer λmax = 664 nm. The adsorption
capacity and removal efficiency (%) were calculated using Eq. (1) and 2,
respectively.
v(C0 − Ct )
q= (1)
m
(C0 − Ce )
Removal efficiency(%) = 100 (2)
C0
where C0, Ce and Ct = initial, equilibrium, and after time t concentrations
of the adsorbate (mg/L); v = solution volume (L); and M = mass of
adsorbent (g).
The adsorption mechanism, kinetics, and thermodynamic of the MB
removal process were correlated by two different kinetics (pseudo-first-
order and pseudo-second-order), adsorption isotherms (Langmuir and
Freundlich and thermodynamics models, respectively. Response Surface
Methodology (RSM) was employed to evaluated the optimization of
different parameters governing the adsorption process and based on
Box-Behnken design (Design Expert 11.1.0.1) [19]. Besides, the effect of
initial MB concentration, contact time, and M/NAT-NC dosage on the
adsorption efficiency was evaluated. Furthermore, the behavior of the
adsorption process was evaluated viz the second-order polynomial
model (Eq.3):
∑ ∑ ∑
n n n− 1 ∑
n
Y = b0 + bi Xi + bii Xi2 + bij Xi Xj (3)
i=1 I=1 i=1 j=i+1
where Y is the projected% removal response of MB, b is a constant, while
Xi and Xj represent the coded values of the variables. bij, bii, and bi be­
longs to the interaction effect coefficient, quadratic coefficient, and
linear coefficient, respectively. Besides, the statistical significance of the
tailored quadratic models was investigated by analysis of variance
(ANOVA) [40]. The fitted models were employed to calculate the opti­
mum adsorption condition (parameters) of the experimental process; by
turn, it was corroborated based on the experimental results. All exper­
iments were conducted in triplicate, and the averaged values were
A. Zenebe et al. Chemical Engineering Journal Advances 8 (2021) 100193

Fig. 1. FT-IR spectra of C. Africana leaf extract (CA), MNPs, MNPs-MB, NAT, M/NAT-NC before and after MB adsorption (a), and the corresponding SEM(EDX)
spectra (b).

4
A. Zenebe et al.
Fig. 2. The powder XRD patterns of MNPs (a), NAT (b), M/NAT-NCs (c).
considered.
Result and discussion
Characterizations
FT-IR analysis
The FT-IR analysis was employed to get insight into the sorbent
synthesis/modification as well as the dye uptake (Fig. 1a and 1b). To
identify the incorporation of CA extract, the spectra of MNPs synthesized
with and without the extract were compared firstly (Fig. 1a). In the FT-
IR spectrum of MNPs, more bands are concentrated in the 400–850 cm− 1
region, attributed to the metal-O adsorption bond. The presence of
MNPs can be confirmed by the strong peaks at 573 cm− 1, 479cm− 1, 444
cm− 1, and 417cm− 1in the FT-IR region, which can be assigned to the
magnetite tetrahedral and octahedral sites stretching mode of the Fe-O.
Whereas the band near 1630 cm− 1 stands for the O–H stretching vi­
bration of surface-adsorbed water molecules on the MNPs [34,37,38,
41].
As can be seen from the FT-IR spectra of CA, a strong stretching band
at 3393 cm− 1 shows the presence of N–H stretching vibration of amine
group NH2, which also overlaps with the -OH stretching vibration due to
water and phenolic group. The sharp peak that appeared at 2924 cm− 1
indicates -C-H stretching vibration of the -CH2 functional group. The
peak at 1650 cm− 1, corresponding to C = O stretching, suggesting the
presence of the -COOH group. Besides, the peak at 1241cm− 1 shows
aromatic C = C stretching, and that at 1056 cm− 1 represents the C–O
stretching of ether [34,38] in phytoconstituents of the extract. Hence,
the presence of these functional groups validates the alkaloids, flava­
nones, or terpenoids molecules of CA (presence of basic and acidic
functional groups).
The FT-IR spectra of NAT show the bands at 3543 cm− 1, 3328 cm− 1,
and 1642 cm− 1, which can be related to the water molecules located
inside the channels of NAT and/or associated with exchangeable cat­
ions. The strong peaks vibrational frequency at the band positioned
1061 and 975 cm− 1 arises from the asymmetric stretching vibration (T-
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Chemical Engineering Journal Advances 8 (2021) 100193
O-T, T = Si, Al). While the bands at 500–800 cm− 1 belong to the pseudo-
lattice vibrations, the bands at 627 and 684cm− 1 of the NAT attributed
to the symmetric stretch (T-O-T) [42,43]. The FT-IR spectra of
M/NAT-NC show the overlapping of the absorption bands of the NAT
and CA; also, similar peaks as MNPs with relatively less intensity
appeared at 573 cm− 1, 479cm− 1, 444 cm− 1, and 417cm− 1. The
appearance of a strong peak at around 633 cm− 1, due to the stretching
bond of Fe–O, signifies the incorporation of MNPs in the composite. In
addition, the intensity of the Si-O/Al-O bands in the M/NAT-NC is
weaker than in NAT, indicating the interaction of Fe-O with the
Si-O/Al-O [34,37]. The above overall characteristics FT-IR spectrum
signifies the association of MNPs, CA, and NAT as composite nano sor­
bents. Furthermore, the presence of carboxyl, carbonyl, and alkene
functional groups (2924 cm− 1, 1650 cm− 1, and 1241cm− 1) demon­
strates the electrostatic, ionic, and covalent type interaction (chemically
bonding) between the CA and the positively charged MNPs. Thus, it
could be proposed that these functional groups in the leaf extract might
be acting as a reducing and stabilizing agent in the formation of MNPs.
These FT-IR signals signifying the synthesis of the nano sorbents were
further supplemented by XRD and UV–vis signals in the section which
follows. To get evidence on the incorporation of MB dye into the com­
posite sorbent, the sample solid after equilibrium treatment time was
investigated (Fig. 1b). For the sample after dye treatment, there exist
different shifts on the characteristic absorption spectral band of
M/NAT-NC compared to before treatment. The main shifts were from
3326 cm-1 to 3324 cm-1, 3199 cm-1 to 3222 cm-1 1633 cm-1 to 1635
cm-1, 1065 cm-1 to 1061 cm-1, 983 cm-1 to 979 cm-1 and from 633
cm-1 to 627 cm-1. It should be attributed to the incorporation of MB dye
into the active sites of the nanocomposite sorbent.
Moreover, as can be seen from the SEM (EDX) spectra of CAMNPs
(Fig. 1), all the characteristics signal spectra for Fe, Cl, C, O suggesting
the functionalization by polymer from the CA extract into the MNPs.
Meanwhile, the characteristic additional signals belongs to Si, and most
intense spectra of O than that of CAMNPs appeared in M/NAT-NC
spectra. This phenomenon is attributed to the incorporation of NAT.
Furthermore, the new spectral signal belongs to the N atom was
A. Zenebe et al.
Fig. 3. UV-Visible absorption spectra of MNPs and M/NAT-NCs(a), and pHpzc for M/NAT-NCs(b).
contained only in the case of M/NAT-NC-MB, owing to the adsorption of
MB dye in the nanocomposite.
Powder XRD analysis
The powder MNPs, NAT, and M/NAT-NC XRD patterns were stipu­
lated in Fig. 2. The XRD pattern revealed the diffraction peaks at 2θ =
30.59◦ , 35.95 o, 43.64 o, and 57.58 o respectively indexed to (220),
(311), (400) and (511) planes of the face-centered cubic crystal phase of
MNPs (JCPDS. 75–0449) and confirmed the crystalline nature of the
synthesized MNPs (Fig. 2a). It is consistent with the analysis by Prasad
et al. (39) and Baseri and Tizro, (36). As shown in Fig. 2b, the charac­
teristic diffraction peaks at 2θ = 13.66 o, 15.16 o, 19.34 o, 20.44 o, 21.59
o
, 28.29 o, 31.46 o, 35.01 o, 37.22 o, 41.55 o, and 50.85◦ could be
assigned to the crystal planes (220), (111), (400), (311), (420), (511),
(531), (711), (600) and (771), respectively at the crystal phase of NAT
(JCPDS. 19–1185). However, the characteristics peak of both NAT and
MNPs phases have appeared at 2θ = 13.69◦ , 21.63◦ , 50.94 o, and at 2θ =
35.83◦ , 57.49◦ (Fig. 2c), indicating that the M/NAT-NC was successfully
synthesized by impregnation method [45]. Moreover, the average
crystalline size of the green synthesized CAMNPs (17.4 nm), NAT (19.7
nm), and M/NAT-NC (19.7 nm) was calculated using Debye Scherrer’s
equation (Eq.4), signifies the nanosized nature of the composite parti­
cles. The reflectance peak position and relative intensities were
approximately matched within the standard magnetite of MNPs, con­
firming the inverse cubic spinel structure [44,45].
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Chemical Engineering Journal Advances 8 (2021) 100193
(4)
where λ is the CuKα irradiation wavelength, D is the mean particle size
of the crystalline domain, β represents the full width at half maximum
intensity (FWHM) of the diffraction peak, and θ is the diffraction angle
of MNPs at (311) peak
The diffuse reflectance of the nanoparticles was investigated to
further confirm the synthesis of MNPs using UV-visible spectral analysis
(Fig. 3a). A strong peak between 2oo nm and 276 nm observed in UV-
visible spectrophotometer is obviously related to the spectral charac­
teristics of Fe metal [26]. This phenomenon suggests surface Plasmon
resonance (vibrations) of the MNPs due to their encapsulation by the
polymer in the extracts. Besides, the presence of magnetite was indi­
cated by the peak at 350 nm. These peaks should be the characteristic
signals for CAMNPs. The results obtained in this study are also in good
agreement with the report of earlier studies where fruit and leaf, and
seed extracts were used [26,39,43]. No other peaks were observed in the
spectrum, indicating the high purity of the synthesized MNPs by this fast
and green method. The UV–Vis spectrum of CAMNPs was masked in the
presence of NAT, as evidenced by the absorption of M/NAT-NC (red
curve). However, with the increase of the wavelength in the range of
200–800 nm, the downward trend in the absorption intensity was
examined. A similar observation has also been reported in the literature
[42].
A. Zenebe et al.
Fig. 4. SEM image of MNPs, NAT, M/NAT-NC (a), and size distribution of M/NAT-NCs (b).
Determination of pHpzc
pHpzc, the value of pH at which the surface of M/NAT-NC became
neutral, was determined as indicated in the previous studies [19,21].
Accordingly, pH 9.0 was found to be a pHPZC (Fig. 3b). When the pH
value was less than the pHPZC, the surface demonstrated a more positive
charge, and the concentration of H+was high. Thus, the protons are
expected to compete with positively charged MB cation for vacant
adsorption sites causing a decrease in dye uptake. Conversely, at the
solution pH > pHPZC, the adsorbent surface is negatively charged and
expected to favors the uptake of cationic dyes due to increased elec­
trostatic force of attraction. Thus, MB adsorption onto M/NAT-NC
would be favored at pH higher than pHPZC. Therefore, the pH values
should be maintained above 9 to ensure a predominant negatively
charged surface.
Surface morphology analysis
SEM analysis gives information about the morphology and textural
properties of synthesized MNPs, NAT, and M/NAT-NC (Fig. 4a).
Consistent with the XRD characteristics pattern discussed above, it was
revealed from the SEM image that the surface morphology of NAT is
cubic and rectangular in shape, it was confirming the characteristic
cubic NAT crystal phase. The SEM image of the CAMNPs consisted of
agglomerated small (nanosized) spherical particles with other particles.
It was observed that the adhered particles were highly aggregated and
resulting in irregular arrangements. Such spherical morphology con­
firms the nano nature of MNPs [38]. Moreover, the incorporation of the
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Chemical Engineering Journal Advances 8 (2021) 100193
MNPs into the NAT framework (M/NAT-NC) resulted in the distortion of
the original rectangular structure of the NAT and increased particle
population. This indicates surface morphological changes and more
population (dispersion) of the composite particles. The particle size
distribution of the M/NAT-NC was estimated from the ImageJ software
(Fig. 4b). As revealed from the deduced area of the particles, there exists
uniform particle distribution with an average diameter of about 17.56
nm.
Adsorption study
Effect of M/NAT-NC dose and contact time
The dye removal efficiency as a function of M/NAT-NC dosage was
examined. As illuminated in Fig. 5a, the MB removal (adsorption) was
enhanced by increasing the dosage of M/NAT-NC from 0.1to 0.5 because
the higher amount of adsorbent dosage gives more adsorption sites.
Also, there might be synergism by the oxidation process induced by the
nanomaterial, which increases with dosage. The optimum conditions for
the removal (98.6%) of MB were pH = 9 and 0.5 g of M/NAT-NC.
However, the optimum MB removal by CAMNP and NAT was 87%
and 83%, respectively. In addition, the contact time was investigated to
find the optimum time for the efficient removal of MB. As can be seen in
Fig. 5b, the adsorption of MB increased as time went on, with 40 min
found to be the point for maximum removal. Beyond 40 min, the
removal of MB became constant, ascribable to the preferential occupa­
tion of all the free adsorption sites. Table 1 shows the comparative
A. Zenebe et al. Chemical Engineering Journal Advances 8 (2021) 100193

Fig. 5. The 3D surface plots showing the effect of different factors in the removal of MB: the M/NAT-NC dose and equilibrium time (a), the concentration of MB and
equilibrium time (b), and concentration of MB and the dose of M/NAT-NC (c).

Table 1 equilibrium time for the adsorption of MB in various adsorbents/

Comparison of equilibrium time (min.) for the adsorption of MB with the liter­ modified adsorbents. M/NAT-NC had shown to have low equilibrium
ature value of various modified MNPs based adsorbents and zeolite. time, even compared with the state-of-the-art absorbents: starch-based
Adsorbent Time Ref. high-performance adsorptive hydrogel (STAH) and layered double hy­
(min) droxides (LDHs adsorbents, although STAH and LDH demonstrated high
Magnetite/Natrolite/Nanocomposite(M/NAT-NC) 40 Present performance [46,47].
Natrolite 80 study
CAMNP 65 Present Effect of initial concentrations of Methylene blue
study
The adsorption efficiency of M/NAT-NC as a function of initial
Present
study concentrations of MB was evaluated. Fig. 5c shows that the adsorption
Zeolite A/Fe3O4 nanocomposite (maize leave extract) 180 [37] efficiency of MB by M/NAT-NC (0.5 g dose) decreased with an increase
Fe3O4 nanoparticles (Zanthoxylum armatum DC 180 [45] of MB initial concentrations (10 to 50 ppm). An initial 10 ppm MB was
extract) found to be the optimum dosage for the highest removal (98.6%) at 40
Clinoptilolite modified by iron oxide nanoparticles 45 [48]
Chabazite 180 [49]
min equilibrium time Hence, the decrease of removal efficiency upon
Synthetic Zeolite 200 [50] increasing MB concentration beyond 40 ppm could be due to the occu­
Clinoptilolite/ montmorillonite and quartz (Natural 820 [51] pation of the M/NAT-NC finite adsorption sites [18]. As can be seen from
Zeolite) Fig. 5c, the adsorbate-adsorbent optimum combination to attain
Natural Zeolite 180 [52]
maximum removal was found to be 0.5 g and 40 ppm at 40 min,
Fe3 O4 /C nanocomposite (carbon-based) 60 [53]
consistent with the result in section 3.2.1.

8
A. Zenebe et al. Chemical Engineering Journal Advances 8 (2021) 100193

Analysis of the adsorption process Fig. 6c were appeared outside the range of the model assumptions,
Optimization of the adsorption variables using statistical approaches suggesting that no more outliers were available. The perturbation plot
is crucial to get a detailed systematic insight into the approach and for design space was investigated to obtain the comparative effect of all
provide evidence for future application of the material. In addition, it the adsorption factors at a particular point in that space (Fig. 6d), which

(5)

gives vibrant evidence about the variables in the adsorption process and
helps to minimize experimental errors [19]. Eq. (5) was applied to
analyze the empirical relationship between the adsorption efficiency of
MB and the experimental parameters.
Where A, B, and C stand for the equilibrium time, M/NAT-NC dose,
MB concentration, respectively. For instance, while the parameters
accountable to increase the% removal of the dye is correlated with the
positive coefficients while as, the negative coefficient suggests the
decrease in the removal efficiency upon raising the parameters, and the
corresponding statistical parameters (ANOVA) were presented in
Table 2.
As can be seen in Table 2, the model p-value (0.0001) and F-Value
(112.7) show the statistical significance and appropriateness to spatial
modeling. In addition, all the investigated parameters in the study (p-
value <0.05) were demonstrated the significance of a 95% confidence
interval, suggesting the feasibility of the model and its appropriateness
to elucidate the correlation between independent variables and the
response [18]. The adjusted R2 (0.9843) was in pair agreement with the
predicted R2 (0.9463), with < 0.2 variations. Model precision (36.94)
measures the signal-to-noise ratio, which was greater than 4, suggesting
the adequacy of the signal to be evaluated by the model (it indicates an
adequate signal).
The validation of model adequacy was evaluated using the diagnostic
plots. As presented in fig Fig. 6a, the linear regression was well fitted to
the actual and predicted MB removal plot. This evidence can be taken as
the manifestation of the model adequacy in explaining the experimental
conditions. Fig. 6b illustrates the plot of a normal plot of residuals, also
called externally studentized residuals versus the% of normal proba­
bility. The studentized residuals are thought to be suitable for outlier
detection [54]. The normal distribution of errors across all runs as well
as the model adequacy for this experiment, can be deduced from the
linear distribution of points in the plot (Fig. 6b). The number of runs that
conduct a t-test for each residual was plotted as a function of externally
studentized residual (Fig. 6c), where the points laying away from the red
limits are designated as outliers [54]. Accordingly, none of the points in
was used to determine the most influential factor in MB removal
(adsorption). Accordingly, the steepest slope for factor B (slope = 14.21)
than A (4.85) and C (− 10.86) could be attributed to more sensitivity of
MB removal to composite dosage than other variables. Particularly, the
relatively flat line belongs to factor "C" can be correlated with minimal
dependence of the dye adsorption on this factor.
Adsorption kinetics
The investigation on the adsorption process kinetics has been used to
get imperative information about the mechanistic and the rate of the
adsorption process and helps to validate its practical application. In the
current study, Pseudo-first-order and Pseudo second kinetic models
were used (Eq. (6) and 7, respectively) [55].
k1
log(qe − qt ) = log qe − t (6)
2.303
t 1 1
= + t (7)
qt k2 q2e qe
Where qe is the content of adsorbed MB at equilibrium (mg g − 1), qt is
the adsorbed MB amount at time t (mg g − 1), and k1 is the MB adsorption
rate constant (min− 1), k2 is the rate constant (g mg− 1 min− 1) of the
pseudo-second-order, and qe is the equilibrium adsorption capacity. The
batch adsorption experiments for kinetic studies were carried out by
adding M/NAT-NC (0.5 g) in 50 ml MB (40 ppm). The kinetic parameters
calculated from both first-order and second-order models (Figs. 8a and
8b) were presented in Table 3. The pseudo-second-order kinetic preva­
lence over the adsorption process was signified by its higher correlation
coefficients (R2) (0.999) than the pseudo-first-order model (0.969), by
turn, suggests that the rate-determining step is predominantly chemi­
sorption [41].
Adsorption isotherm study
The adsorption process, mechanism, and estimation of adsorption
capacities of the M/NAT-NC were determined. To verify the efficiency of

Table 2
The Quadratic model-based ANOVA analysis of MB removal.
Source Sum of Squares Df Mean Square F-value p-value Fit Statistics

Model 3175.27 9 352.81 112.69 < 0.0001 SD = 1.77

Residual 21.92 7 3.13 — — CV(%) = 2.10
Lack of Fit 9.51 3 3.17 1.02 0.4713 R2 = 0.9931 Predicted R2 =0.9463
Pure Error 12.40 4 3.10 — — Adjusted R2 = 0.9843
Terms Coefficients SE Coefficients Mean Square F-value p-value
Constant 87.58 0.7913 — — —
A 3.45 0.6256 352.81 112.69 < 0.0001
B 14.21 0.6256 95.29 30.44 0.0009
C − 10.86 0.6256 1616.25 516.23 < 0.0001
AB 0.5725 0.8847 942.65 301.08 < 0.0001
AC 1.75 0.8847 1.31 0.4187 0.5382
BC 9.08 0.8847 12.32 3.94 0.0877
A2 − 2.67 0.8623 329.79 105.33 < 0.0001
B2 − 5.74 0.8623 30.03 9.59 0.0174
C2 1.13 0.8623 138.52 44.24 0.0003

9
A. Zenebe et al. Chemical Engineering Journal Advances 8 (2021) 100193

Fig. 6. The MB adsorption diagnostic curves of (a) predicted vs. actual (b) the normal plot of residuals, (c) the residual vs. run, and (d) perturbation of factors.

Fig. 7. Pseudo-first order (a) and pseudo-second-order kinetics plots (b) for MB adsorption onto M/NAT-NC.

the adsorption process, the suitability of both Langmuir and Freundlich
isotherm models was correlated to the experimental curve. Langmuir
isotherm is based on the assumption that the adsorption process could
proceed beyond monolayer coverage of adsorbate over homogeneous
adsorption sites [2]. While the Freundlich model is governed by an
empirical equation following the assumption that the adsorption process
takes place on heterogeneous adsorbent surfaces. The completion of
monolayer coverage (the Langmuir model) and Freundlich equation was
verified using linear form equations (Eq.8 and 9, respectively).
1
=
1 1
* +
1
(8)
qe qm b Ce qm
where qm is qe for a complete monolayer (mg/g) and b is a Langmuir
constant related to the energy of adsorption(L/mg).
logqe = logKf + 1/nlogCe (9)
where the Freundlich constants, Kf belongs to the adsorbent adsorption
capacity, and n is an empirical parameter related to the intensity of
adsorption. 1/n can be calculated from the intercept and slope of the plot
of logqe vs logCe. For values in the range 0.1 <1/n <1, adsorption is
favorable. The greater the values of Kf, the better is the favorability of
adsorption. The result of the Langmuir and Freundlich adsorption
isotherm study were presented in Fig. 8 (a and b). As seen from Table 4,
the data fitted well to the Freundlich isotherm model having a

10
A. Zenebe et al. Chemical Engineering Journal Advances 8 (2021) 100193

Fig. 8. The plots of MB adsorption isotherm onto M/NAT-NC: Langmuir (a), Freundlich (b), Vant Hoff’s (c).

Table 3
Pseudo-first and Pseudo-second order constants for MB adsorption on M/NAT-NC.
MB qexp Pseudo-first-order kinetic model Pseudo-second-order kinetic model
qcal (mg/g) k1 (min− 1) R2 qcal(mg/g) k2 (g/mg.min) R2

M/NAT-NC 5.948 2.46 0.122 0.9693 6.097 0.119 0.9998

Table 4 constant as a function of temperature Eq. (10) and (11).

Parameters of Langmuir and Freundlich adsorption isotherms for the adsorption
of MB onto the M/NAT-NC. ΔG0 = − RTlnKa (10)
Adsorbent Langmuir isotherm Freundlich isotherm
ΔS0 ΔH 0
qm b (mg/L) RL R2 Kf 1/n R2
lnKa = − (11)
R RT
M/NAT-NC 30.00 0.807 0.034 0.851 3.196 0.456 0.958
where K is the distribution coefficient expressed as Ka = qe/Ce, T is the
2 2 absolute temperature (K), and R is the gas constant (8.314 J/Kmol). The
correlation coefficient (R ) of 0.958, then Langmuir model with R of
values of ΔH◦ and ΔS◦ were determined from the slope and intercept
0.851. This indicates that the Freundlich model is more suitable to
between lnKa and1/T as shown in Fig 8c. The obtained data reflected
describe the relationship between the amounts of MB molecules (10–50
that increasing the temperature from 298 K to 318 K was accompanied
mg/L initial concentration) adsorbed by the adsorbents used in the
present study, consistent with the kinetic result. If such kinetics of dye
uptake was more inclined to pseudo-second-order (chemosorption), the
Table 5
fact that the Freundlich isotherm model was fitted to the phenomena
Thermodynamic parameters for MB adsorption on M/NAT-NC at different
could be related to the formation of multilayer sorbed MB due to more temperatures.
strength of chemical interaction than that of physical type.
S. No Thermodynamic Temperature (K) Thermodynamic values
parameters M/NAT-NC
Adsorption thermodynamics 1 ∆Go(kJ/K) 298 1.139
308 - 3.121
The thermodynamic parameters, such as the standard Gibbs free 318 - 7.381
energy (ΔG◦ ), standard enthalpy change (ΔH◦ ), and the standard en­ 2 ΔH0(kJ/K) 128.087
3 ΔS0(kJ/K) 0.426
tropy change (ΔS◦ ), can be determined by the changes in the equilibrium

11
A. Zenebe et al.
Fig. 9. Recycling efficiency of M/ NAT-NC on MB removal.
by increased adsorption capacity, indicating the endothermic nature of
dye adsorption. The Gibbs free energy change (∆G˚) and other thermo­
dynamic parameters were summarized in Table 5. The positive values of
∆H˚ and ∆S˚ show that the adsorption process is endothermic with
increasing the randomness of the system. The negative value of free
energy indicates that the adsorption process is spontaneous. Also, this
phenomenon seems to be in pair agreement with the kinetic result as
such spontaneity could be taken as the manifestation of chemical
interaction, although spontaneity is not always prerequisite for chemical
interaction/adsorption or oxidation. Moreover, the more negative free
energy value with the rise in temperature suggesting the feasibility of
the adsorption process at higher temperatures. It is consistent with the
results reported earlier [18,53].
Regeneration of adsorbent
The regeneration study of the M/NAT-NC was performed to test the
ability of the adsorbent to validate the reusability of the nanocomposite.
Accordingly, desorption of MB from exhausted M/NAT-NC was evalu­
ated (Fig. 9). It was achieved by shaking M/NAT-NC by shaking it with
HCl solution (0.1 N) for 40 min. Afterward, the particles were separated
by employing an external magnet, which was then washed with ultra­
pure water several times to remove the HCl and desorbed components.
Finally, the regenerated M/NAT-NC was further reused three times for
the adsorption of MB at the optimum conditions and was found to have
removal efficiencies very close to fresh adsorbents [56].
Conclusion
Natrolite incorporated nanocomposites (M/NAT-NC) were success­
fully synthesized through impregnation of magnetite nanoparticles
functionalized with CA leaf extract and used for the treatment of MB-
contaminated water. The UV–Vis, XRD, FT-IR and, SEM analyses were
conducted to examine the adsorbent morphology and functional groups.
The material was found to endows high dispersion and magnetic prop­
erties. The batch technique was used to study the adsorption as a
function of various influencing factors such as initial dye concentration,
contact time, temperature, pH, and adsorbents dosage. The obtained
results indicated enhanced adsorption of MB with increasing the amount
of adsorbent dosage and contact time until the optimum values and
decreases with increase the amount of initial dye concentration. The
optimum adsorption efficiency of M/NAT-NC for MB removal from the
water was explored at different parameters using Response Surface
Methodology (RSM) based Box-Behnken Design (BBD), and it was found
to be a valuable tool. The optimum conditions for maximum% removal
were found to be 98.6% at 40 min, 0.5 g M/NAT-NC, 40 mg/L, and
pH=9. The survey of kinetics, equilibrium isotherm, and thermody­
namic studies corroborated that the MB adhesion on M/NAT-NC was
12
Chemical Engineering Journal Advances 8 (2021) 100193
fitted best with the pseudo-second-order Freundlich model, as well as
the spontaneity of the process, respectively. It worth noting that M/
NAT-NC could be reasonably used for treating MB from aqueous envi­
ronments due to high adsorption and easy and quick separation. It was
confirmed from the regeneration experiments that the exhausted M/
NAT-NC had reflected relatively similar removal efficiency as the new
one.
Declaration of Competing Interest
The authors declare no competing interests.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (21507149, 51338010), and Arba Minch University research
and development fund.
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