Silveira2017 Environmental Technology Carole 2017

Environmental Technology
ISSN: 0959-3330 (Print) 1479-487X (Online) Journal homepage: http://www.tandfonline.com/loi/tent20
Iron-oxide Nanoparticles by Green Synthesis

Method Using Moringa oleifera Leaf Extract for
Fluoride Removal
Carole Silveira, Quelen Letícia Shimabuku, Marcela Fernandes Silva &

Rosângela Bergamasco
To cite this article: Carole Silveira, Quelen Letícia Shimabuku, Marcela Fernandes Silva
& Rosângela Bergamasco (2017): Iron-oxide Nanoparticles by Green Synthesis Method
Using Moringa oleifera Leaf Extract for Fluoride Removal, Environmental Technology, DOI:
10.1080/09593330.2017.1369582
To link to this article: http://dx.doi.org/10.1080/09593330.2017.1369582
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Download by: [Australian Catholic University] Date: 21 August 2017, At: 02:06
Publisher: Taylor & Francis & Informa UK Limited, trading as Taylor & Francis Group
Journal: Environmental Technology
DOI: 10.1080/09593330.2017.1369582
Iron-oxide Nanoparticles by Green Synthesis Method Using Moringa oleifera Leaf
Extract for Fluoride Removal
Carole Silveira1, Quelen Letícia Shimabuku2, Marcela Fernandes Silva3, Rosângela
Bergamasco4
Downloaded by [Australian Catholic University] at 02:06 21 August 2017
1
Department of Chemical Engineering, State University of Maringá, Avenida Colombo,
5790. Bloco D90, 87020–900, Maringá, Paraná, Brazil. e-mail: carole_silveira@hotmail.com
2
Department of Chemical Engineering, University of West Parana, street of Faculdade,
645, 85903–000, Toledo, Paraná, Brazil. e-mail: le.shimabuku@gmail.com
3
5790. Bloco D90, 87020–900, Maringá, Paraná, Brazil. e-mail: celafs@gmail.com
4
5790. Bloco D90, 87020–900, Maringá, Paraná, Brazil. e-mail: rbergamasco@uem.br
Abstract
The aim of this work was to synthesize iron-oxide nanoparticles (NPsFeO) via a non-polluting method
(green synthesis), using Moringa oleífera leaf extract, and evaluate its fluoride ion adsorption
potential, comparing its efficiency with a commercially available adsorbent (activated carbon of bone
[BGAC]). The adsorbent materials were characterized using X-ray diffraction, transmission, and
scanning electronic microscopy, X-ray dispersive energy spectrometry, and N2 adsorption/desorption.
The results showed that the fluoride ion adsorption is favorable in neutral pH values, with maximum
adsorption at pH 7 for NPsFeO, and pH 5 for the BGAC. Adsorption kinetics tests showed that the
equilibrium was reached in 40 min for the NPsFeO, and 90 min for BGAC, with adsorption potential
of 1.40 mg g-1 and 1.20 mg g-1, respectively. The model that best described the kinetic data was
pseudo-first-order for NPsFeO and pseudo-second-order for BGAC. The Langmuir isotherm had a
better fit for both adsorbents. The thermodynamic parameters indicated spontaneous and endothermic
adsorption at 30, 40, and 50° C for BGAC, and at 30°C for NPsFeO. The regeneration process showed
that is possible to reuse NPsFeO three times in the fluoride ion adsorption process. As a result of its
adsorption capabilities and the shortest contact time to achieve equilibrium, the synthesized
nanoparticles in this work are a highly promising material for fluoride ion removal.
Keywords: Iron oxide nanoparticles; Green synthesis; Moringa oleifera; Water treatment;
Fluoride
Funding
The authors gratefully acknowledge CAPES (Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior) for its financial support.
1. Introduction
Fluoride is an element found in water, in the concentration range of 0.5–1.5 mg L-1,
and has benefits for human health. However, water consumption at concentrations above
that value for extended periods of time can cause skeletal fluorosis, dental, neurological
diseases, and affect fetal brain function, among others. [1, 2, 3]. Among the available
methods for fluoride ion removal from water, we can mention coagulation-precipitation [4],
electrochemical processes [5], Ion Exchange [6], membrane separation [7] and adsorption [8].
The adsorption process stands out for its simple application and provides satisfactory results
for the removal of fluoride ions [7].

Several adsorbents have already been evaluated for water-fluoride removal, among
them: activated alumina, biosorbents, resins, calcium-based adsorbents, and activated
charcoal. [9, 10, 11]. Nanotechnology has been widely addressed in relation to adsorption
processes due to its differentiated characteristics, such as the large surface area available
compared to the small volume of the particles. Nanoparticles of iron oxides can be easily
synthesized, and are used in the preparation of different adsorbents for the adsorption of
cations, anions, organic components, among other substances present in contaminated water
[12, 13].
Among the most used methods for the metal nanoparticles synthesis hydrothermal
synthesis can be cited [14]. It´s a chemical approach in which metal ions in the solution are
reduced in conditions that favor the subsequent formation of clusters or metal aggregates on
the nanometer scale [15, 16]. Plant extracts can be used in green synthesis processes, and can
act as reducing agents for the development of metallic nanoparticles [17, 18]. It is known that
the source of the plant extract can influence the nanoparticles characteristics. This occurs
because different extracts contain different concentration combinations of organic reducing
agents [19]. It is believed that the principal active agents in some of these syntheses are the
polyphenols present, for example, in tea, wine, red=grape bagasse, pomegranate leaf, and
Moringa oleífera. The green synthesis of nanoparticles provides an advance over other
methods because it is simple and inexpensive, relatively reproducible, and often results in
more stable materials [20, 21, 22].
The Moringa oleífera is a plant of the Moringaceae family, and is native to India,
Pakistan, Bangladesh, and Afghanistan. [23] used the Moringa oleífera flower extract to
synthesize hydroxyapatite nanoparticles, crystalline calcium phosphate. [24] synthesized
nanoparticles of zinc oxide using Moringa oleífera leaf extract as a reducing agent. [21]
studied the green synthesis of gold nanoparticles using Moringa oleífera petal extract as a
reducing agent. This study presents the synthesis of iron-oxide nanoparticles (NPsFeO) using
Moringa oleífera extract, and its use in fluoride ion adsorption, comparing its adsorption
efficiency with a commercial adsorbent of granulated charcoal of bone (BGAC).
2. Materials and methods
2.1. Adsorbents
NPsFeO adsorbent was prepared from iron nitrate III (Fe(NO3)3.9H2O) synthesized
by green synthesis using Moringa oleífera leaf. The commercially available adsorbent
(BGAC), from the Bonecher company, was used for comparison.
2.1.1. Synthesis of NPsFeO using Moringa oleifera leaf extract
The green synthesis of NPsFeO has been described by Shahwan, Abu Sirriah [25] and
by Huang, Weng [26]. In this study, the Moringa oleífera leaf extract was prepared by heating
an aqueous mixture of leaves to 80° C, in a 60 g L-1 concentration, for 1 hour. Then the
extract was vacuum-filtered. Then, a solution of 0.1 M of iron nitrate III was added to the
Moringa oleífera extract, with 99.10% purity in a 1:2 (v/v) ratio under stirring. It was possible
to visualize the NPsFeO formation immediately by the color change of the mixture, from
green to black. NPsFeO separation was first made by water evaporation at room temperature,
then by drying at 50° C in an oven.
2.2. Fluorinated Solution

A fluoride standard solution of 1.000 mg L-1 was prepared by dissolving 2.21 g of NaF
(P.A.) in distilled water and, from this, dilutions were made of the initial concentration of 6
mg L-1 [27, 28].
2.3. Adsorbents characterization
The NPsFeO and BGAC were characterized by X-ray diffraction (XRD),
Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM),

energy dispersive X-ray Spectrometry (EDX), and N2 adsorption/desorption by BET method.
Diffractograms of the adsorbents were obtained for the structural characterization of
the samples using a diffractometer (Bruker-AXS D8, Advance). A copper emission radiation
source (CuKα, λ = 0.154 nm), 40 kV voltage, 30 mA current, and 2θ scan ranging from 15 °
to 75 °, with a 2 ° min-1 step, were used. The diffractograms were interpreted using a JCPDS
87-1166 diffraction pattern. The NPsFeO size was estimated using the Scherrer equation
(Equation 1).
⁄ (1)
In this equation is the radiation wavelenght, 0.89 is the constant related to the
spherical shape approximation, B is the width of the peak at half height, and B is the Bragg
angle [29].
Morphological characteristics were analyzed by TEM. The adsorbent samples were
deposited in a sample port (grid) of Cu (200 mesh), and covered with a thin film of pure
carbon (CF200-Cu, EMS) in JEM-1400, with JEOL equipment 120 kV. Using SEM the
adsorbent samples were fixed on metallic disks, and then covered with a thin film of gold
using Quanta 250 - Fei, coupled with an EDX system (Oxford Instruments x-act).
Adsorption/Desorption of N2 (77 K) were estimated in a gas-sorption analyzer
(Quantachrome Autosorb 1® volumetric analyzer) to verify the textural characteristics of the
samples, such as the specific surface area (SBET), average pore diameter (Dp), and pore
volume (VP).
2.5. Adsorption of fluoride ions in NPsFeO and BGAC

All tests explained as follows were performed for the NPsFeO and BGAC adsorbents.
The effect of pH on the adsorption was analyzed using 0.5 g adsorbent mass and a volume of
50 mL of solution with 6 mg L-1 concentration. The pH values were varied at 3, 4, 5, 7, and
10, using HNO3 (1 mol/L) and/or NaOH (0.1 mol/L). During the batch adsorption process, the
solutions with the adsorbents were placed in sealed containers in a Dubnoff bath (304-TPA),
at 130 rpm agitation for 6 hours, then they were vacuum-filtered and read in a UV-Vis
spectrophotometer using the SPADNS method—4500–F- D.—Standard Methods [30].
Adsorption kinetics tests were conducted using 0.5 g adsorbent mass and 50 mL of
solution, with a fluoride concentration of 6 mg L-1, pH 5.0 for BGAC, and pH 7.0 for
NPsFeO. Samples were placed in a bath, with agitation of 130 rpm and 25° C, and drawn at
different time intervals, filtered, and the final concentration of fluoride ions determined.
The adsorption isotherm tests were performed at pH 5.0 for BGAC, and pH 7.0 for
NPsFeO, with fluoride concentration of 6 mg L-1, and the adsorbent mass was varied between
0.05 and 0.5 g. The solutions with the adsorbents were stirred at 130 rpm in the bath until
equilibrium time was reached, and the final concentration of fluoride ions was determined.
2.6. Regenaration of NPsFeO
The regeneration of NPsFeO was investigated in order to evaluate the possibility of
reuse of the adsorbent in the fluoride ion adsorption process. The methodology used was
described by [31]. After impurity removal the adsorbent was tested in three successive reuses.
NPsFeO was cleaned by washing with a 20% ethanol solution. The mixture was stirred for 10
min at room temperature. After washing, the supernatant was removed by magnetic
separation, and the wash was repeated three times.

3. Results and discussions
The results are presented that were obtained for the characterizations of the
adsorbent materials NPsFeO and BGAC, and the fluoride ions adsorption results in these
adsorbents.
3.1. Adsorbents Characterization
Diffractograms obtained by XRD of NPsFeO and BGAC are shown in Figure 1. The
diffractograms were used to the structural/compositional characteristic determinations of the
samples. For the sample BGAC (Figure 1a) shows that the main phosphorus phase is the
hydroxyapatite (bone charcoal consists of 76% CaHAP (Ca10(PO4)6(OH)2) [32]. The NPsFeO
sample (Figure 1b), despite the high noise level, caused by scattering due to the use of a
copper source, it is possible to observe characteristic peaks at 30.3º, 33º, 35.6º, 43.4º , 49.5°,
54.5°, 57.5°, and 62.8°, for diffraction planes of iron oxide in the hematite (α-Fe2O3)
structural form, according to the diffraction pattern JCPDS 87-1166 [33]. The NPsFeO
average diameter was estimated at 7nm by the Scherrer equation (Equation 1).
Figure 1 near here
The morphologies of the adsorbents were analyzed by means of SEM, the
magnitude being 20000x in relation to the real size of NPsFeO and BGAC. The micrographs
and EDX spectra are presented in Figure 2.

Figure 2 near here
As can be seen in Figure 2a, the NPsFeO synthesized using Moringa oleífera leaf
extracts presented spherical agglomerated. Some particle agglomerates can also be observed
due to magnetic properties [34]. Similar results were obtained by other authors [35]. The
BGAC presents a porous and irregular structure (Figure 2c), which is a typical characteristic
of activated materials [36]. The NPsFeO EDX pattern (Figure 2.b) detected the predominant
presence of Fe and O, and a small percentage of K and Ca. The presence of oxygen indicates
the formation of Fe oxide nanoparticles, as previously demonstrated by XRD. The presence of
K and Ca originated from the compounds present in the Moringa oleífera leaf [37]. The EDX
spectrum of BGAC (Figure 2d) showed high values of calcium and phosphorus due to the
main phase being hydroxyapatite [32].
The TEM micrographs of NPsFeO and BGAC are shown in Figure 3.
Figure 3 near here

Micrographs of NPsFeO (Figure 3. a) show that the particles have an average
diameter of less than 100nm. As can be seen, the obtained particles have nanometric
structures, in which small particles associate themselves, forming darker coloration
agglomerates, which are characteristic of metallic particles [38, 39]. These images confirmed
that the green synthesis using Moringa oleífera leaf extract is efficient in obtaining iron
compound nanoparticles. In the activated charcoal sample (Figure 3. b) only grayish
formations of hydroxyapatite crystals are noticed [40]
The textural characterization parameters were estimated by the N2

adsorption/desorption method (77 K), and showed that the specific surface areas (SBET) were
133.9 m2 g-1 and 99.79 m2 g-1, with a pore volume of 0.3283 and 0.0870 cm3 g-1 for the BGAC
adsorbent and the NPsFeO, respectively. The mean pore diameters for the BGAC were 9.80
nm and 4.14 nm for the NPsFeO, which characterizes the predominance of mesopores.
Figure 4 shows the adsorption/desorption isotherms of N2 corresponding to adsorbent
materials. According to the IUPAC classification, the observed isotherms of type III and V for
BGAC (Figure 4a) are related to very weak interactions in systems containing macro and
mesopores, whereas those of type IV for NPsFeO (Figure 3.b), are related to the presence of
hysteresis and are characteristic of mesopores, which confirms the results previously found
[41, 42].
Figure 4 near here
3.2. Adsorption tests
The pH of the solution is one of the main factors that can influence the adsorption
capacity by affecting the adsorbents’ surface charge [43]. To determine the most favorable
chemical condition for the fluoride ion adsorption on the activated carbon and NPsFeO,
adsorption studies were performed at different pH values (3, 5, 7, and 10). In Figure 5 it is
possible to observe that the adsorption was influenced by the pH of the environment. So, for
all subsequent adsorption tests, pH 7 was adopted for NPsFeO, and pH 5 for BGAC, with
maximum adsorption capacities of 1.40 and 1.47 mg g-1, respectively. Other authors have
also used this pH range for fluoride ion removal [44, 45, 46]. According to studies reported in
the literature [47, 48], in an alkaline environment the hydroxyl groups will compete with
fluorine ions at the active site of the adsorbent, reducing the adsorption potential to basic pH.
Figure 5 near here
Defluoridation kinetic tests were performed to determine the adsorbents’ equilibrium
point. Figure 4 shows the fluoride ion kinetic adsorption behavior in NPsFeO and BGAC,
using an aqueous solution of 6 mg L-1 fluoride.
Figure 6 near here
The adsorption process was fast at the beginning of the process, due to a large number
of active sites available for adsorption. Over time the adsorbate removal decreased, reaching
equilibrium point at 40 min when NPsFeO was used, and 180 min for the BGAC, with an
adsorption capacity of 1.40 mg g-1 for NPsFeO and 1.20 mg g-1 for the BGAC. The adsorption
capacity of both adsorbents was similar, but the adsorbent synthesized in this work was
equilibrated in a significantly shorter time than BGAC.
To analyze the adsorption process mechanism, the data obtained in the kinetic tests
were adjusted for the following nonlinear models: pseudo-first-order—this model assumes
that the adsorbate removal rate of in relation to time is directly proportional to the difference
in saturation concentration, and the number of active sites present in the adsorbent [49, 50].
Pseudo-second order it is assumed that the adsorption capacity of the adsorbent depends on
the number of active sites occupied in the same [51], represented by Equations 2 and 3, using
OringinPro 9 64-bit software.
(2)
⁄ (3)
where and are pseudo-first-order and pseudo-second-order rate constants,
respectively, is the amount of ions adsorbed at time t, and is the adsorption capacity at
equilibrium. The parameters of the abovementioned models and the ratio coefficients for
adsorption of fluoride ions are shown in Table 1.
Table 1 near here
The results suggest that the fluoride adsorption processes were well represented by
both the pseudo-first-order model and the pseudo-second-order model, with r2 values varying
from 0.996–0.999. However, for the process using BGAC, the experimental qeq value and the
derivative of the pseudo-second order model are different, according to García-Sánchez,
Solache-Ríos [52]. This means that fluoride adsorption is a first-order reaction.
The adsorption isotherm is important for estimating the affinity between adsorbent and
adsorbate, and the maximum adsorption capacity. [36, 53]. The fluoride ion adsorption
experimental data using NPsFeO and BGAC were adjusted for the Langmuir, Freundlic,
Temkin, Toth, Sips, and Redlich-Paterson models (Table 2), in order to better understand the
adsorption behavior. The experimental data with model adjustments are shown in Figure 7
and the adjusted parameter values for each isotherm, as well as the correlation coefficient r2,
are shown in Table 3.
Table 2 near here

Figure 7 near here
Table 3 near here
The results indicate that the experimental data of adsorption isotherms for BGAC and
NPsFeO have been described for all models (Langmuir, Freundlic, Temkin Toth, Sips and
Redlich-Paterson), since the correlation coefficients vary from 0.9482 to 0.9868 (Table 3).
However, the Langmuir isotherm defines a better fit for both BGAC and NPsFeO, with a
correlation coefficient of 0.9824 and 0.9868, and maximum adsorption capacity for the lowest
adsorbent mass used of 4.13 and 4.44 mg g-1, respectively, which implies the adsorption of
fluoride ions is homogeneous and monolayer, and that adsorption only occurs in a fixed
number of equivalent and well-defined sites, accommodating only one adsorbed atom.
The parameter is an important datum provided by the Langmuir isotherm, which
relates the Langmuir affinity constant (b), through Equation 4, and provides the solute affinity
degree by the sites of the adsorbent material.
⁄ (4)
where b is the Langmuir isothermal constant, and C0 is the concentration of fluoride
ions (mg g-1). For both adsorbents studied the values of RL were calculated, and the values are
shown in Figure 8. The equilibrium parameters presented values greater than zero and less
than one, indicating that the fluoride ion adsorption process is favorable, since for RL> 1, the
process is unfavorable, for = 1 it is linear, for 0 < <1 it is favorable, and for =0 it is
irreversible [54].
Figure 8 near here
Analyzing the adsorption capacity of the nanoparticles synthesized in this work
(NPsFeO), and comparing with other adsorbents already used for the removal of fluoride ions
(Table 4), it can be observed that the NPsFeO presented a higher pollutant adsorption capacity
in some cases, proving to be a good alternative for the removal of fluoride ions.
Table 4 near here
3.3. Thermodynamic Study in Adsorption Process
The main purpose of the thermodynamic study is to determine whether the process is
spontaneous, endothermic, or exothermic. To calculate the free energy of Gibbs for the
fluoride ion adsorption process at temperatures of 30, 40, and 50° C, the enthalpy (ΔH°) and
entropy (ΔS°) parameters in Equations 5 and 7 were used [55].
(5)
(6)
⁄ ⁄ ⁄ (7)
in which ΔG° is the Gibbs free energy variation, ΔH° is the enthalpy variation, ΔS° is
the entropy variation, R is the ideal gas constant, T is the absolute temperature in kelvin, and
K is the constant of balance. The thermodynamic adsorption parameters are shown in Table 5.
Table 5 near here
The ΔG° indicates the degree of spontaneity of the adsorptive process.
The negative values found for the fluoride ions adsorption using BGAC confirm the
spontaneity of the process, and the thermodynamic viability for all the analyzed temperatures
[56]. For the NPsFeO it can be observed that the process is only spontaneous at the lowest
temperature. The endothermic nature of the process can be verified by the positive values of
ΔH° for the two adsorbents. However, the positive value found for ΔS° in the BGAC process
suggests an increase in the degree of randomness at the solid-liquid interface, in the
adsorption of fluoride ions. For the NPsFeO, the negative ΔS° implies the fact that the
fluoride ion molecules decrease their randomness, increasing the interaction of the adsorbate
with the adsorbent.
3.4. NPsFeO regeneration

Based on the results of the adsorption tests (better adsorption capacity and lower
equilibration time), the regeneration was only done for NPsFeO as the adsorbent of interest in
the present study.
After using NPsFeO in the fluoride ion adsorption process, these were washed with
20% ethanol solution to determine the reuse potential of the adsorbent. Adsorption tests show
that it is possible to reuse the NPsFeO three times (Figure 9), compared to the control sample
(qeq of fluoride ion removal before washing). A reduction of 80.94% to 80.44% can be
observed in the adsorption potential after the first wash, and 75% in the following washes.
According toOkoli, Boutonnet [31] the decrease in adsorption efficiency may have occurred
due to the incomplete removal of the fluoride ion from the surface of NPsFeO. The major
advantage of regenerating NPsFeO is the reduction in the adsorption process cost.
Figure 9 near here
4. Conclusion
In the present study, iron-oxide nanoparticles were successfully synthesized using
Moringa oleífera leaf extract by green synthesis. Its efficiency was tested in the adsorption
process of fluoride ions in a batch system, comparing it with a bone activated charcoal
commercial adsorbent
The characterization techniques showed that the adsorbent materials are porous with a
predominance of mesopores, and with an irregular surface for the BGAC and spherical forms
for NPsFeO. In addition, the EDX and XRD spectra confirmed the formation of iron-oxide
nanoparticles.
In the evaluation of batch process adsorbents, NPsFeO obtained a higher efficiency,
with equilibrium time reached in 40 min, and an adsorption capacity of 1.40 mg g-1 at pH 7,
compared to BGAC that reached equilibrium time in 180 min, and whose maximum
adsorption capacity was 1.20 mg g-1 at pH 5. The adsorption experimental data of both
adsorbents showed a good fit for the Langmuir isotherm, with correlation coefficients equal to
0.9868 and 0.9824 for NPsFeO and BGAC, respectively. The parameter indicated that the
fluoride ion adsorption process is favorable for the two adsorbents studied
The regeneration study of NPsFeO shows that even though a reduction of the
adsorption capacity occurs after the first washing, the reuse of the same in the process is
possible, which can lead to a cost reduction.
Based on the results obtained in this work, it can be concluded that the green synthesis
of iron-oxide nanoparticles was successful and could be a favorable alternative for the
environment. Besides its easy application, there is no need to use chemicals, high
temperatures, and pressure. In addition, it presented an excellent adsorption capacity for
fluoride ions, compared to the commercial adsorbent.
Acknowledgements
The authors are grateful to COMCAP/UEM (Complexo de Centraisde Apoio à
Pesquisa) for DRX, TEM and SEM analyses.
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Figure 1. Diffractograms obtained by XRD of adsorbents: a) BGAC; and b) NPsFeO
Figure 2 a) NPsFeO micrographs obtained by SEM; b) NPsFeO spectrum obtained by

EDX; c) BGAC micrographs obtained by SEM; d) BGAC spectrum obtained by EDX.
Figure 3. Micrographs obtained by TEM: (a) NPsFeO; (b) BGAC
Figure 4. N2 adsorption-desorption isotherm: (a) BGAC; (b) NPsFeO
Figure 5. Effect of pH on removal of fluoride ions by NPsFeO and BGAC (pH range of
3–10; concentration of fluoride ions solution 6 mg L-1).
Figure 6. Adsorption of fluoride ions by NPsFeO and BGAC as a function of time:

experimental and simulated data by pseudo-first and pseudo-second order kinetic
models (C0 = 6 mg L−1, m = 0,5 g, Agitation = 130 rpm, T = 25 °C).
Figure 7. Batch process adsorption isotherm, experimental data fitted to Langmuir,

Freundlic, Temkin Toth, Sips and Redlich-Paterson models: a) BGAC; b) NPsFeO.
Figure 8. Effect of initial concentration of adsorbents BGAC and NPsFeO on adsorption

of fluoride ions on RL values
Figure 9. Regeneration of NPsFeO after fluoride ion adsorption test

Table 1. Kinetic parameters of fluoride ion adsorption by NPsFeO and BGAC
Kinetic model Adsorbent
NPsFeO BGAC
qexperimental (mg g-1) 1.40 1.20
Pseudo-first order model
K1 (1 min-1) 0.175 0.016
qeq (mg g-1) 1.421 1.280
r2 0.996 0.998
Pseudo-second order model
-1 -1
K2 (g min mg ) 0.016 0.011
qeq (mg g-1) 1.452 1.538

r2 0.999 0.990
Table 2. Langmuir, Freundlich, Temkin Toth, Sips, and Redlich-Paterson isothermal
models.
Application and
Isotherm Expression
Characteristic
Homogeneous
surfaces
Langmuir ⁄ Mono Layer
Two theoretical
parameters
Heterogeneous
surfaces
Freundlich
Multi-layer
Two empirical
parameters
Mono layer
Temkin ⁄ chemisorption
Two theoretical
parameters
Heterogeneous
surfaces
Toth [ ⁄ ⁄ ]
Multi-layer
Three empirical
parameters
Combined
Langmuir – Freundlich
Sips [ ⁄ ]
Three semi-
empirical parameters
Paterson
Redlich-
[
⁄
]
surfaces
parameters
Heterogeneous
Three empirical
Table 3. Parameters of adsorption isotherm of fluoride ions by NPsFeO and BGAC
Langmuir Freundlich Temkin Toth Sips Redlich-
qmax=
qmax=
9.629
qmax= 6.824 KF= 2.162 B= 1.256 8.667 kRP= 4.42
bs= 0.8321
b=0.4960 nF= 0.607 kT=7.471 bT=0.5803 n= 0.749
Ks=
R2=0.9824 R2= 0.9727 R2=0.9482 nT=0.5649 R2= 0.97
0.3010
R2=0.9740
R2=0.9747
qmax=8.66 qmax=9.62
qmax=6.036 KF=2.162 B=1.256 7 9 kRP=4.42
b=0.680 nF=0.607 kT=7.4715 bT=0.580 bs=0.832 n=0.749

2 2 2
R =0.9868 R =0.9804 R =0.9628 nT=0.565 Ks=0.301 R2=0.981
R2=0.9816 R2=0.9822
Table 4. Adsorption capacity of different adsorbents
Adsorbent qmax (mg g-1) Reference
Nanoparticle of iron
compounds modified with Moringa
4.44 In this work
oleifera leaf
Bone Charcoal 4.13 In this work

Magnetite modified with Al 0.43
[46]
Magnetite modified with La 0.46
Activated Alumina 0.76 [49]
Granular Ceramics 0.99 [50]

Granular ceramics modified
with FeSO4 – 7H2O 0.47
[51]
Granular ceramics modified 0.26
with Fe2O3
Hydrous ferric oxide 6.71 [52]
Table 5. Thermodynamic parameters of fluoride ion adsorption using NPsFeO and
BGAC
ΔG° (kJ / mol) ΔH° (kJ / mol) ΔS° (kJ / mol K)
T (K)=303 T=313 T=323
BGAC -3.50337 -4.30964 -6.06234 35.10753 0.126938
NPsFeO -4.30345 3.92034 3.49347 123.8703 -0.39906

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Iron-oxide Nanoparticles by Green Synthesis

Carole Silveira, Quelen Letícia Shimabuku, Marcela Fernandes Silva &

To link to this article: http://dx.doi.org/10.1080/09593330.2017.1369582

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Journal: Environmental Technology

Iron-oxide Nanoparticles by Green Synthesis Method Using Moringa oleifera Leaf

Extract for Fluoride Removal

Carole Silveira1, Quelen Letícia Shimabuku2, Marcela Fernandes Silva3, Rosângela

5790. Bloco D90, 87020–900, Maringá, Paraná, Brazil. e-mail: carole_silveira@hotmail.com

645, 85903–000, Toledo, Paraná, Brazil. e-mail: le.shimabuku@gmail.com

5790. Bloco D90, 87020–900, Maringá, Paraná, Brazil. e-mail: celafs@gmail.com

5790. Bloco D90, 87020–900, Maringá, Paraná, Brazil. e-mail: rbergamasco@uem.br

scanning electronic microscopy, X-ray dispersive energy spectrometry, and N2 adsorption/desorption.

The authors gratefully acknowledge CAPES (Coordenação de Aperfeiçoamento de Pessoal de

Nível Superior) for its financial support.

Fluoride is an element found in water, in the concentration range of 0.5–1.5 mg L-1,

for the removal of fluoride ions [7].

them: activated alumina, biosorbents, resins, calcium-based adsorbents, and activated

because different extracts contain different concentration combinations of organic reducing

more stable materials [20, 21, 22].

synthesize hydroxyapatite nanoparticles, crystalline calcium phosphate. [24] synthesized

efficiency with a commercial adsorbent of granulated charcoal of bone (BGAC).

2. Materials and methods

(BGAC), from the Bonecher company, was used for comparison.

2.1.1. Synthesis of NPsFeO using Moringa oleifera leaf extract

then by drying at 50° C in an oven.

2.2. Fluorinated Solution

mg L-1 [27, 28].

2.3. Adsorbents characterization

The NPsFeO and BGAC were characterized by X-ray diffraction (XRD),

Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM),

energy dispersive X-ray Spectrometry (EDX), and N2 adsorption/desorption by BET method.

Diffractograms of the adsorbents were obtained for the structural characterization of

Morphological characteristics were analyzed by TEM. The adsorbent samples were

Adsorption/Desorption of N2 (77 K) were estimated in a gas-sorption analyzer

(Quantachrome Autosorb 1® volumetric analyzer) to verify the textural characteristics of the

2.5. Adsorption of fluoride ions in NPsFeO and BGAC

50 mL of solution with 6 mg L-1 concentration. The pH values were varied at 3, 4, 5, 7, and

spectrophotometer using the SPADNS method—4500–F- D.—Standard Methods [30].

The regeneration of NPsFeO was investigated in order to evaluate the possibility of

separation, and the wash was repeated three times.

3. Results and discussions

3.1. Adsorbents Characterization

diffractograms were used to the structural/compositional characteristic determinations of the

Figure 1 near here

The morphologies of the adsorbents were analyzed by means of SEM, the

and EDX spectra are presented in Figure 2.

Figure 2 near here

the formation of Fe oxide nanoparticles, as previously demonstrated by XRD. The presence of

main phase being hydroxyapatite [32].

The TEM micrographs of NPsFeO and BGAC are shown in Figure 3.

Figure 3 near here

structures, in which small particles associate themselves, forming darker coloration

compound nanoparticles. In the activated charcoal sample (Figure 3. b) only grayish

formations of hydroxyapatite crystals are noticed [40]

The textural characterization parameters were estimated by the N2

Figure 4 shows the adsorption/desorption isotherms of N2 corresponding to adsorbent