molecules

Article
Influence of the Alcoholic/Ethanolic Extract of Mangifera indica
Residues on the Green Synthesis of FeO Nanoparticles and
Their Application for the Remediation of Agricultural Soils
Jhordi Bautista-Guzman 1 , Rosa Gomez-Morales 1 , David Asmat-Campos 2, * and Noemi Raquel Checca 3

1 Facultad de Ingeniería, Carrera Ingeniería Ambiental, Universidad Privada del Norte, Trujillo 13011, Peru;
jhordibautista@outlook.com (J.B.-G.); rosarush1999@gmail.com (R.G.-M.)
2 Dirección de Investigación e Innovación, Universidad Privada del Norte, Trujillo 13011, Peru
3 Brazilian Center for Physics Research, R. Dr. Xavier Sigaud 150, Rio de Janeiro 22290-180, Brazil;
nomifsc@gmail.com
* Correspondence: david.asmat@upn.edu.pe or davidasmat88@hotmail.com

Abstract: The green synthesis of iron oxide nanoparticles (FeO NP) has been investigated using the
extract in absolute ethanolic and alcoholic solvents 96% from the peel of the mango fruit (Mangifera
indica), thus evaluating the influence of the type of solvent on the extraction of reducing metabolites.
A broad approach to characterization initially controlled by UV-vis spectrophotometry has been
directed, the formation mechanism was evaluated by Fourier transform infrared spectroscopy (FTIR),



the magnetic properties by characterization by Physical Property Measurement System (PPSM), in


addition to a large number of techniques such as X-ray energy dispersive spectroscopy (EDS), X-ray
Citation: Bautista-Guzman, J.; diffraction (DRX), transmission electron microscopy (TEM/STEM), electron energy loss spectroscopy
Gomez-Morales, R.; Asmat-Campos, (EELS), and Z potential to confirm the formation of FeO NP. The results suggest better characteristics
D.; Checca, N.R. Influence of the for FeO NP synthesized using 96% alcoholic solvent extract. The successful synthesis was directly
Alcoholic/Ethanolic Extract of proven in the removal of metals (Cr-VI, Cd, and Pb) as a potential alternative in the remediation of
Mangifera indica Residues on the
agricultural soils.
Green Synthesis of FeO Nanoparticles
and Their Application for the
Keywords: FeO nanoparticles; green synthesis; Mangifera indica; soil remediation; metal removal
Remediation of Agricultural Soils.
Molecules 2021, 26, 7633. https://
doi.org/10.3390/molecules26247633

Academic Editor: Sergio Navalon

1. Introduction
In recent years the use of nanoparticles (NP) has attracted the attention of the scientific
Received: 1 November 2021 community due to their profitability [1], efficiency [2], and a variety of physicochemical
Accepted: 10 December 2021 characteristics [3] as hollow colloidal nanoparticles that have pores for integral use of
Published: 16 December 2021 the surface and volume in order to carry out biological, physical, and chemical activi-
ties [4]. Likewise, they have a wide field of application such as in the textile industry [5],
Publisher’s Note: MDPI stays neutral nanomedicine [6], soil remediation, water [7], and transformation and detoxification of
with regard to jurisdictional claims in a wide variety of environmental pollutants such as chlorinated organic solvents, poly-
published maps and institutional affil- chlorinated biphenyls (PCBs), nitrates, bacteria, hydrocarbons, and heavy metals [8]. The
iations. synthesis methodology of iron oxide nanoparticles (FeO NP) can occur from different
materials, but many of the adverse effects are associated with toxicity, due to the presence
of absorbed substances on the surface of the nanoparticles [9–11]; in these cases, some
work uses new mechanisms such as ‘nano zero valent’ iron nanoparticles (nZVI) that
Copyright: © 2021 by the authors. are stored in nitrogen gas to avoid oxidation during the synthesis or drying [12–14]. On
Licensee MDPI, Basel, Switzerland. the contrary, an oxygenic atmosphere favors the generation of magnetic NP Fe (Fe3 O4
This article is an open access article and Fe2 O3 ) which stand out for their high specific surface and absorbent capacity, and
distributed under the terms and due to their magnetism they enable the extraction of particles through external magnetic
conditions of the Creative Commons fields [15,16] and nanoparticles with superparamagnetic properties [17,18].
Attribution (CC BY) license (https:// Thus, eco-friendly alternatives are methods using microorganisms, enzymes, fungi,
creativecommons.org/licenses/by/
and plant or fruit extracts. On the latter, there are investigations using Parthenocissus
4.0/).

Molecules 2021, 26, 7633. https://doi.org/10.3390/molecules26247633 https://www.mdpi.com/journal/molecules

Molecules 2021, 26, 7633 2 of 17

quinquefolia [19], green tea [20], coconut shell [21], eucalyptus [22], Moringa oleifera [23],
and Bauhinia tomentosa [24]. The development of these ecosystem-friendly methods for
nanoparticle synthesis has become an important branch of nanotechnology: “green synthe-
sis” [25,26]. Plant or fruit extracts contain phytochemicals and metabolites that give them
unique properties, which can be used as reducing agents for the synthesis and stabilization
of nanoparticles [13,27].
According to [28], the synthesis of iron nanoparticles supported with bentonite ob-
tained sizes between 40–80 nm, and the analysis of the nanomaterial shows the presence
of C, O, and Fe, attributing the former to molecules and polyphenols of green tea extract.
The absorption of Cr (VI) in sandy loam soil was stable up to a concentration of 100 mg/L;
subsequently it decreased as a result of the availability of active sites for the adsorption
of Cr, deducing an increase in the particle dose for higher concentrations of pollutant.
The estimated pH to achieve good results is between 2–6 on the acid scale, and [29] ob-
tained iron nanoparticles and carried out a comparative analysis of chemically synthesized
nanoparticles with extracts of neem and mint leaves; the removal of lead and nickel at a
concentration of 0.1 g NP/Kg of soil shows that the NP by NaBH4 removed 21.6% Pb and
18.5% Ni; while with neem extract 26.9% Pb and 33.2% Ni. The low removal efficiency
is the product of agglomeration and exposure to the atmosphere resulting in oxidation
of the surface of the particles. In the case of mint leaves, a concentration of 0.2 g NP/Kg
of soil and the elimination of 66.1% Pb and 56.1% Ni was obtained. The improvement in
performance is due to the little agglomeration between the nanomaterial, unlike the others,
increasing the reaction area [30]. In the case [31] synthesized iron oxide nanoparticles with
Excoecaria cochinchinensis extract which were applied to eliminate arsenic in soils, for the
SEM-EDS characterization, nanoparticles between 50 and 100 nm with Fe compounds were
evidenced, O, C product of the reduction mechanism. The BET surface area was 32 m2 .g−1
and had a mean pore diameter of 12 nm, indicating high adsorption capacity. The adsorp-
tion of As occurred in the amorphous and crystalline Fe oxide layer, due to its positive
charge that could adsorb both arsenate and arsenite simultaneously. FeO NP was obtained
using Excoecaria cochinchnensis Lour extract with sizes between 5 and 20 nm with different
carbon-oxygen functional groups on the surface of the Fe3 O4 spheres, which contribute
to the adsorption of Cd, and on the surface of the particles by electrostatic attraction. The
adsorption rate was 93.69% at 30 min. The change in pH exerts variation in the removal
of Cd (II): at low pH the elimination of Cd (II) decreases by increasing the temperature,
indicating that the adsorption process is an exothermic process. Furthermore, an increased
dose of nanoparticles and low temperature increase the adsorption rate [32]. Nanoparticles
have a size between 38–47 nm and it was shown that they can oxidize As (III) to As (V)
almost completely at 24 h, with pH values 3 and 7. On the contrary, [33] investigated the
elimination of As (V) with nanoparticles synthesized with green tea extract which have a
size between 50 and 100 nm, irregular and amorphous, and during the adsorption of As
(V) the amount of active sites were reduced.
The objective of this research is to evaluate the influence of the solvent (96% alcohol
and absolute ethanol) in the extraction of metabolites from the residues (shell) of Mangifera
indica for its application as an organic reducer in the synthesis of FeO nanoparticles;
likewise, the nanoparticulate material will be applied in the removal of metals present in
agricultural soil such as hexavalent chromium (Cr-VI), cadmium (Cd), and lead (Pb).

2. Materials and Methods

2.1. Materials
Iron nitrate (Fe (NO3 )3 9H2 O) (CAS: 7782-61-8, Merck, Germany) and absolute ethanol
(CAS No. 64-17-5) were purchased from Merck Millipore, while alcohol 96% GL of the
national chain of pharmacies ‘MiFarma’, in Peru. The samples of ripe mango (M. indica var.
Edward) were acquired from a local supermarket in the city of Trujillo, Peru. Ultrapure
water (Thermo Scientific, Barnstead Smart2Pure, Waltham, MA, USA) was used throughout
the investigation.
 var. Edward) were acquired from a local supermarket in the city of Trujillo, Peru. Ul-
trapure water (Thermo Scientific, Barnstead Smart2Pure, Waltham, MA, USA) was used
Molecules 2021, 26, 7633 throughout the investigation. 3 of 17

2.2. Treatment of M. Indica Husk

The M. indica
2.2. Treatment of M.fruits
indicawere
Huskwashed with ultrapure water to remove impurities. Subse-
quently, the peel was peeled and separated. From a total of six mango units (2.08 kg), 307.7
The M. indica fruits were washed with ultrapure water to remove impurities. Sub-
g of wet peel was obtained, which was dried in a forced convection oven UNPA—MEM-
sequently, the peel was peeled and separated. From a total of six mango units (2.08 kg),
MERT model UM 55 plus (Memmert GmbH Co. KG. Schwabach, Germany) for 15 h at
307.7 g of wet peel was obtained, which was dried in a forced convection oven UNPA—
temperature of 75 °C to eliminate the humidity present. After the established time, we
MEMMERT model UM 55 plus (Memmert GmbH Co. KG. Schwabach, Germany) for 15 h
proceeded to crush, finally obtaining 34.11 g of powdered shell. The sample was stored at
at temperature of 75 ◦ C to eliminate the humidity present. After the established time, we
4 °C in a refrigerator
proceeded for use
to crush, finally in subsequent
obtaining 34.11 gprocedures.
of powdered shell. The sample was stored at
4 ◦ C in a refrigerator for use in subsequent procedures.
2.3. Obtaining Alcoholic Extract 96%/Absolute Ethanolic
2.3. Obtaining
With what Alcoholic Extract 96%/Absolute
was previously obtained, anEthanolic
aliquot of 5 g was taken of M. indica ground
beingWith
diluted,
whatinwas
twopreviously
beakers, with 50 mLanofaliquot
obtained, alcoholofat5 96%
g was G.L. andof50
taken M.mL of absolute
indica ground
ethanol.
being Second,
diluted, in each sample was
two beakers, withsubjected
50 mL oftoalcohol
magnetic stirring
at 96% G.L.(CAT-M6)
and 50 mLinofbeakers
absoluteat
300 RPM Second,
ethanol. for 30 min. The
each mixtures
sample waswere then placed
subjected in test tubes
to magnetic and
stirring subjectedin
(CAT-M6) tobeakers
an elec-
tric300
at centrifuge
RPM for(Hettich
30 min. Zentrifugen,
The mixturesEBA
were20C)
thenat placed
3000 RPM for tubes
in test 15 min. Subsequently,
and subjected to the
an
supernatants were filtered with a diaphragm vacuum pump (GAST DOA-P704-AA);
electric centrifuge (Hettich Zentrifugen, EBA 20C) at 3000 RPM for 15 min. Subsequently, fi-
nally,
the it was stored
supernatants at filtered
were 4 °C, covered
with a with aluminum
diaphragm foil to
vacuum pumpavoid undesirable
(GAST reactions
DOA-P704-AA);
and its it
finally, subsequent
was storeduse 4 ◦FeO
at of NP. with aluminum foil to avoid undesirable reactions
C, covered
and its subsequent use of FeO NP.
2.4. Green Synthesis of Iron Oxide Nanoparticles with Alcoholic 96% and Absolute Ethanolic
2.4. Green
Solvent Synthesis of Iron Oxide Nanoparticles with Alcoholic 96% and Absolute Ethanolic
Extracts
Solvent Extracts
For the synthesis in the green route (Figure 1), 100 mL of the precursor iron nitrate
For the synthesis in the green route (Figure 1), 100 mL of the precursor iron nitrate
nonahydrate (Fe (NO3)9H2O) 0.1 M was prepared, which was distributed in volumes of
nonahydrate (Fe (NO3 )9H2 O) 0.1 M was prepared, which was distributed in volumes of
50 mL for each synthesis. Next, 6 mL of each extract was added dropwise in 96% alcoholic
50 mL for each synthesis. Next, 6 mL of each extract was added dropwise in 96% alcoholic
and absolute ethanolic solvents respectively, and it was kept under constant stirring of
and absolute ethanolic solvents respectively, and it was kept under constant stirring of
400 RPM at room temperature. Subsequently, the solutions obtained were subjected to
400 RPM at room temperature. Subsequently, the solutions obtained were subjected to heat
heat in an electric stove until reaching 120 °C. For this, the beaker with the mixture was
in an electric stove until reaching 120 ◦ C. For this, the beaker with the mixture was placed
placed in a larger baker glass with water up to half. Finally, the mixing beaker was re-
in a larger baker glass with water up to half. Finally, the mixing beaker was removed when
moved when the liquid content was consumed in order to obtain solid nanoparticles.
the liquid content was consumed in order to obtain solid nanoparticles.

Figure 1. Block
Figure 1. Block diagram
diagram of
of the
the green
green synthesis
synthesis process
process of
of FeO
FeO NP
NP mediated by M.
mediated by M. indica
indica extract.
extract.

2.5. Characterization of Iron Oxide Nanoparticles (FeO NP)

The absorbance spectra of FeO NP were obtained by UV-vis spectrophotometry
(Hewlett Packard, 8452, Palo Alto, CA, USA) in the range of 300 to 900 nm, in order
to find the typical wavelength of plasmon resonance surface (RPS) on iron oxide nanostruc-
tures, as well as to evaluate the stability of the nanoparticles over time. Additionally, the
samples were analyzed using a Nicolet iS50 FT-IR infrared spectrometer (Thermo Fischer
Molecules 2021, 26, 7633 4 of 17

Scientific) to evaluate the organic agents present in the extracts and FeO NP and to respond
to possible mechanisms involved in the formation of nanostructures. Electron microscopy
analyses were performed using a Transmission Electron Microscopy (TEM) in the modes:
High Resolution TEM (HRTEM), Scanning TEM (STEM), and Energy-Dispersive X-ray
Spectroscopy (EDS) to characterize the morphology and elemental composition of the
FeO nanoparticles. The studies were conducted in a JEOL 2100F equipment, operating
at an accelerating voltage of 200 kV/current 130 µA and equipped with an CCD camera
(One view). STEM images were obtained using an annular dark field (ADF) detector. The
elemental composition was investigated by EDS using the STEM-DF mode and an Energy
spectrometer of Oxford (Xplore).
The microscope was also equipped with electron energy loss spectroscopy (EELS)
(EELS-GIF Tridiem GATAN) accessories. EELS spectra were conducted in the STEM
imaging mode using a spot size of 0.7 nm. The spectrometer aperture was 5 mm. The
energy resolution measured by the FWHM of the zero loss peaks was approximately 1.6 eV.
For TEM observation, the nanoparticles were placed inside a 1.5 mL tube with acetone
and ultrasonicated for 30 min. The acetone solution was then dropped over carbon-covered
TEM grids.
X-ray diffraction patterns of the nanoparticles were obtained in an Empyrean diffrac-
tometer (Panalytical) with Cu-Kα radiation (λ = 1.54056 Å) at 45 kV and 40 mA. Data were
collected in the 20◦ < 2θ < 80◦ range in Bragg Brentano geometry, in spinner mode, with a
step size of 0.026◦ .
The stability of FeO NP was characterized by Potential Zeta using the Zeta plus—Zeta
potential analyzer equipment from the Brookhaven Instrument Corporation, from their
electrophoretic mobility. These data are reported as a standard deviation and average of
10 different measurements.
Magnetic properties were measured using a Physical Property Measurement System
(PPMS) DynaCool of Quantum Design at CBPF. The magnetization versus temperature
measurements were performed in zero field cooled (ZFC) and field cooled (FC) conditions
with a 200 Oe probe field. The hysteresis loops were measured at range 5 K and 300 K with
an applied field up to 9 T.

2.6. Removal of Cr-VI, Cd and Pb Present in Agricultural Soil

Samples of 125 g of soil (from cultivation areas of the district of Moche, Trujillo in
Peru), each diluted in 250 mL of ultrapure water, were worked. In order to evaluate the
influence of the FeO NP volume on the removal of metals, a total of three samples C1 = 5 mL,
C2 = 10 mL, and C3 = 15 mL were considered, the same ones that were volumetric with
ultrapure water up to a 50 mL value. Subsequently, the samples were taken to the magnetic
stirrer at 250 RPM for 30 min to obtain a correct homogenization between the FeO NP
and the contaminated soil. Then, a 5 mL aliquot was taken from each of the samples, to
which 10 mL of aqua regia (HNO3 + 3HCl) 1 M was added, and they were made up with
deionized water until reaching a volume of 50 mL respectively. They were then subjected
to the digestion method until the volume was reduced to 10 mL for approximately 50 min.
Finally, the samples were volumetric with ultrapure water, up to the initial volume (50 mL),
and were filtered with a diaphragm vacuum pump, until they were free of impurities.
In addition, they were analyzed in the Atomic Absorption Spectrophotometer (Agilent
Technologies, 200 series AA) for their reading.

3. Results and Discussion

3.1. UV-Vis Spectrum Analysis
Characterization by UV-vis spectrometry was considered as a preliminary analysis to
show a synthesis of nanoparticles.
The reduction of the precursor agent upon exposure to the extracts in the mentioned
solvents is followed by characterization by UV-vis spectrophotometry, the spectra of which
are shown in Figure 2.
 3.1. UV-Vis Spectrum Analysis
Characterization by UV-vis spectrometry was considered as a preliminary analysi
to show a synthesis of nanoparticles.
The reduction of the precursor agent upon exposure to the extracts in the mentioned
Molecules 2021, 26, 7633 solvents is followed by characterization by UV-vis spectrophotometry, the 5 of spectra
17 o
which are shown in Figure 2.

1.2

1.0
FeO NP with alcoholic extract 96%
FeO NP with absolute ethanol extract
0.8

Absorbance (u.a)
0.6

0.4

0.2

0.0

-0.2
400 500 600 700 800
Wavelenght (nm)
Figure2.2.UV-vis
Figure UV-visspectrum
spectrum of FeO NP NP
of FeO obtained by the
obtained bygreen route, using
the green route,extracts of M. indica
using extracts in indica in
of M.
different
differentsolvents.
solvents.The inset
The shows
inset the colloids
shows FeO NP
the colloids FeOobtained.
NP obtained.

The results indicate the presence of the RPS peak at 390.4 and 391.2 nm for FeO NP
The results indicate the presence of the RPS peak at 390.4 and 391.2 nm for FeO NP
syntheses using 96% alcoholic and absolute ethanolic solvent extracts respectively, typical
syntheses using 96% alcoholic and absolute ethanolic solvent extracts respectively, typica
for this type of nanostructure. There is also evidence of a difference between the bandwidths
for this
and type of nanostructure.
the absorbance, the FeO NP sampleThere is also evidence
obtained of a difference
with an extract in absolute between
ethanolicthe band
widths and the absorbance, the FeO NP sample obtained with
solvent being predominant, which shows a higher production of nanostructures, but at an extract in absolute eth
anolic
the same solvent
time a being predominant,ofwhich
high polydispersity showsresults
sizes. These a higher production
certify of nanostructures
the visual perception
of
butthe
atcolor change
the same of the
time solution
a high from light brown
polydispersity to black
of sizes. Theseand describe
results the the
certify formation
visual percep
of FeO NP using M. indica extract, this being consistent with
tion of the color change of the solution from light brown to black and describe the UV-vis spectra of the the for
nanoparticles under study.
mation of FeO NP using M. indica extract, this being consistent with the UV-vis spectra o
Evaluating the stability over time is an important factor to identify the viability of the
the nanoparticles under study.
synthesis of nanostructures.
Evaluating the stability over time is an important factor to identify the viability of the
In Figure 3a,b, spectra are presented as a result of the sequential evaluation from day
1synthesis of nanostructures.
of the synthesis to day 39 of the FeO NP. The results suggest a good behavior in the
projection of the3a,b,
In Figure RPS spectra
peak onare the presented as a result
axis wavelength, which of leads
the sequential evaluation
us to consider that it isfrom day
1 of the
highly synthesis
stable in both to day 39
extracts, butofwith
the aFeO
slightNP. The results
improvement by suggest a good
the alcoholic behavior
solvent 96%. in the
projection of the RPS peak on the axis wavelength, which leads us to consider that it i
However, there is dynamic activity in the absorbances since the values increase compared
to the first
highly day,inwhich
stable both means that
extracts, there
but with is aa slight
processimprovement
of formation of bymore nanoparticles,
the alcoholic solvent 96%
possibly due to the fact that the green synthesis methodology does
However, there is dynamic activity in the absorbances since the values increase compared not usually have
a total reduction efficiency of the precursor, which generates a greater production of
to the first day, which means that there is a process of formation of more nanoparticles
nanostructures and therefore an increase in absorbance. For this case, Figure 3b shows a
possibly due to the fact that the green synthesis methodology does not usually have a tota
higher absorbance value.
reduction efficiency
Polyphenols of the precursor,
are generally believed to which generatesfora the
be responsible greater production
synthesis of nanostruc
and stabiliza-
turesofand
tion irontherefore an increaseand
oxide nanoparticles in absorbance.
are producedFor this case, Figure
by complexing 3b shows
with the a higher ab
Fe salt and
sorbance value.
simultaneous reduction of Fe (III) with oxidized polyphenols [34].

3.2. Fourier Transform Infrared Spectroscopy—FTIR

Functional groups play a very important role in green synthesis. Therefore, to identify
the involvement of these functional groups, the FTIR analysis was carried out before and
after the synthesis of FeO NP using M. indica extract with the solvents under study.
Molecules 2021,2021,
Molecules 26, x26,
FOR PEER REVIEW
7633 6 of
6 of 1718

1.4
1.0
(a) 1.2 (b)
0.8 1.0
Day 01 Day 01

Absorbance (u.a)
Absorbance (u.a)

0.6
Day 04 0.8 Day 04
Day 14 Day 14
Day 25 0.6 Day 25
0.4 Day 32 Day 32
Day 39 0.4 Day 39
0.2
0.2

0.0 0.0

-0.2 -0.2
400 500 600 700 800 400 500 600 700 800

Wavelenght (nm) Wavelenght (nm)

Figure 3. Evaluation
Figure of the
3. Evaluation stability
of the of of
stability FeO NP
FeO NPbyby
UV-vis
UV-visspectrophotometry:
spectrophotometry: (a)
(a) with extract
extract in
inalcoholic
alcoholicextract
extract96%
96%and
and
(b) with extract
(b) with in absolute
extract ethanolic
in absolute ethanolicextract.
extract.

The FTIR spectra

Polyphenols of the synthesized
are generally believed toFeO NP using extracts
be responsible for theinsynthesis
96% alcoholic solvent
and stabiliza-
and absolute ethanolic are shown in Figure 4. The samples show peaks
tion of iron oxide nanoparticles and are produced by complexing with the Fe salt and in highly coincident
ranges withreduction
values between 3371 andoxidized −1 which evidence the presence of OH
3387 cmpolyphenols
simultaneous of Fe (III) with [34].
stretching and aromatic and aliphatic CH respectively, 1697–1726 cm−1 corresponding
to the stretching vibrations of the C=C and C=O bonds respectively. Likewise, there is
3.2. Fourier Transform Infrared Spectroscopy—FTIR
a fairly noticeable peak in both samples at 1352 and 1382 cm−1 , which is linked to the
Functional
presence groupsphosphates
of calcium play a veryand important
CO androleC=Oingroups,
green synthesis.
which canTherefore, to iden-
be evidenced in
tifythe
thecharacterization
involvement ofby these
EDX. The aforementioned peaks disappear when analyzingbefore
functional groups, the FTIR analysis was carried out the
and FeOafter
NPthe synthesis
samples, of FeO
which NPallow
would usingusM.toindica extract with
approximate the solvents
the mechanism of under study.
formation of
The FTIR spectra
nanostructures of the synthesized
and specifically associatedFeOwithNP theusing extracts
functional in 96%
groups C=C alcoholic
and C=O solvent
that
and derive from ethanolic
absolute water-soluble
are compounds such as4.flavonoids,
shown in Figure The samples terpenoids considered
show peaks protective
in highly coinci-
ligands of NPs [35,36]. Mango, being a fruit of tropical climate,
dent ranges with values between 3371 and 3387 cm which evidence the presence of
Molecules 2021, 26, x FOR PEER REVIEW −1 has a quantity of theseOH
7 of 18
compounds
stretching andincluding
aromaticothers such as flavonoids,
and aliphatic gallates,1697–1726
CH respectively, benzophenones, and derivativesto
cm−1 corresponding
−1
theofstretching
gallic acidvibrations
[37]. The peaks
of theat 788and
C=C andC=O
796 cmbondsare associated with
respectively. the vibration
Likewise, there is of the
a fairly
FeO NP.
noticeable peak in both samples at 1352 and 1382 cm , which is linked to the presence of
−1

calcium phosphates and CO and C=O groups, which can be evidenced in the characteri-
100 EDX. The aforementioned peaks disappear when analyzing the FeO NP sam-
zation by
ples, which
90
would allow us to approximate the mechanism of formation of nanostructures
and specifically associated with the functional groups C=C and C=O that derive from wa-
80 compounds such as flavonoids, terpenoids considered protective ligands of
Transmittance (%)

ter-soluble
NPs [35,36].
70 Mango, being a fruit of tropical climate, has a quantity of these compounds
including others such as flavonoids, gallates, benzophenones, and derivatives of gallic
60
acid [37]. The peaks at 788 and 796 cm−1 are associated with the vibration of the FeO NP.
50

40 FeO NP - Absolute ethanolic extract

FeO NP - 96º alcoholic extract
30

20
500 1000 1500 2000 2500 3000 3500 4000
Wave number (cm -1
)

Figure4.4.FTIR
Figure FTIRspectra
spectraofofFeO
FeONP
NPusing
using96%
96%alcohol
alcoholsolvent
solventextract
extractand
andabsolute
absoluteethanol.
ethanol.

3.3. X-Ray Diffraction—XRD

The X-Ray Diffraction (XRD) method was used to investigate the material structure
of the iron nanoparticles. Characterizations were obtained for both synthesis conditions,
which are shown in Figure 5. The diffractogram shows in both cases strong peaks in the
2θ region at 35.6°, 54.2°, 63.1° that are linked to the planes (311), (422), (440). These peaks
are indexed to the magnetite (Fe3O4) magnetic phases with a slight contribution from the
 20
500 1000 1500 2000 2500 3000 3500 4000
Wave number (cm -1
)
Molecules 2021, 26, 7633 7 of 17
Figure 4. FTIR spectra of FeO NP using 96% alcohol solvent extract and absolute ethanol.

3.3. X-Ray Diffraction—XRD

3.3. X-ray
The Diffraction—XRD
X-Ray Diffraction (XRD) method was used to investigate the material structur
The
of the X-Ray
iron Diffraction (XRD)
nanoparticles. method was used
Characterizations wereto obtained
investigatefor
theboth
material structure
synthesis conditions
of the iron nanoparticles. Characterizations were obtained for both synthesis
which are shown in Figure 5. The diffractogram shows in both cases strong peaks in th conditions,
which are shown
2θ region in Figure
at 35.6°, 5. Thethat
54.2°, 63.1° diffractogram
are linkedshows
to theinplanes
both cases strong
(311), (422),peaks
(440).inThese
the peak
2θ region at 35.6◦ , 54.2◦ , 63.1◦ that are linked to the planes (311), (422), (440). These peaks
are indexed to the magnetite (Fe3O4) magnetic phases with a slight contribution from th
are indexed to the magnetite (Fe3 O4 ) magnetic phases with a slight contribution from the
maghemite
maghemite phasephase (γFe
(γFe 2O3). Our results are analogous to previous studies that address th
2 O3 ). Our results are analogous to previous studies that address the
greensynthesis
green synthesisof of
FeOFeO
NPNP [2,38,39].
[2,38,39].

(a) FeO NP - absolute ethanolic extract

Intensity

(b) FeO NP - 96º alcoholic extract

20 25 30 35 40 45 50 55 60 65 70 75 80
2θ(°)
Figure5.5.Characterization
Figure Characterization by by
XRD of FeO
XRD NP synthesized
of FeO with extracts
NP synthesized in solvents
with extracts (a) ethanolic
in solvents (a) ethanoli
absolute, (b) alcoholic 96%.
absolute, (b) alcoholic 96%.

The average crystallite sizes calculated from the FeO NP using the full width at
The average crystallite sizes calculated from the FeO NP using the full width at hal
half maximum intensity (FWHM) of the dominant peak in combination with the Debye-
maximum
Scherrer intensity
equation were(FWHM) of the
3.95 and 2.93 nm,dominant peak
for the FeO in combination
NP cases synthesizedwith
with the Debye-Scher
extract in
absolute ethanolic solvent and alcoholic 96% respectively, which follow the same trend of
the estimated sizes determined by STEM.

3.4. Elemental Composition

The elemental analysis of the FeO NP by both methods was confirmed by the X-
ray energy dispersive spectroscopy (EDS) analysis shown in Figure 6. The spectra show
iron and oxygen peaks which indicate the presence of nanostructures of iron oxide with
good relationship with XRD characterization. In the case of the sample using an extract
in absolute ethanolic solvent, a higher content of iron (29%) is evidenced compared to
the case of extract in alcoholic solvent 96% (23.7%), in both cases with a high oxygen
content; in addition, at the first case, phosphorus and calcium were found, which was also
evidenced in the FTIR characterization both in the extract and with a minimal reduction in
the nanostructure. For the second case in question, no other elements were observed in
the spectrum, which indicates the formation of pure NP Fe in oxide form, which was also
verified in the results by FTIR where this peak disappears remarkably.
 solute ethanolic solvent, a higher content of iron (29%) is evidenced compared to the case
of extract in alcoholic solvent 96% (23.7%), in both cases with a high oxygen content; in
addition, at the first case, phosphorus and calcium were found, which was also evidenced
in the FTIR characterization both in the extract and with a minimal reduction in the
Molecules 2021, 26, 7633
nanostructure. For the second case in question, no other elements were observed in8 of the
17
spectrum, which indicates the formation of pure NP Fe in oxide form, which was also
verified in the results by FTIR where this peak disappears remarkably.

Figure
Figure6. 6.EDS
EDSspectrum
spectrumofofiron
ironoxide
oxidenanoparticles
nanoparticlessynthesized using M.
synthesizedusing M. indica extract (a,b,e,g) absolute
absolute ethanolic
ethanolicsolvent,
solvent,
(c,d,f,h)
(c,d,f,h) 96%96% alcoholic
alcoholic solvent.
solvent.

ItItshould
shouldbe
bementioned
mentionedthat
that iron
iron in
in its
its metallic
metallic form tends to react naturally
naturally with
with air
air
(or water), which generates the formation of an iron oxide
(or water), which generates the formation of an iron oxide layer layer [40].

3.5.
3.5.Transmission
TransmissionElectron
ElectronMicroscopy
MicroscopyTEM/STEM
TEM/STEM
The
The shape and size of the FeO nanoparticles synthesized
shape and size of the FeO nanoparticles synthesized byby the
the green
green pathway
pathway were
were
confirmed by TEM/STEM characterization. Figure 7a corresponds to
confirmed by TEM/STEM characterization. Figure 7a corresponds to the colloid obtainedthe colloid obtained
by usingM.
byusing M.indica
indicaextract
extractininabsolute
absoluteethanolic
ethanolicsolvent,
solvent,and
andthe
theimage
imageisisshown
showninindifferent
differ-
magnifications, where the spherical morphology is evidenced and with
ent magnifications, where the spherical morphology is evidenced and with an approxi- an approximate
size
mate 3.18of±3.18
ofsize 0.51± 0.51
nm. nm.
In the first
In the image
first image (5 (5
nmnmscale)
scale)agglomerates
agglomerates are are observed that
observed that
are linked to organic materials present in the extract, this was also evidenced
are linked to organic materials present in the extract, this was also evidenced in the XRD in the XRD
diffractograms where there was a peak at 2θ at 26.2◦ attributable to organic stabilizing
agents, in addition to the organic radicals shown in the FTIR.
The TEM image related to the FeO NP sample using 96% alcoholic solvent extract is
presented in Figure 7b, where spherical morphology is also evidenced with an average size
of 2.50 ± 0.47 nm.
The histogram shows the particle distribution and the mean size obtained. These
dimensions coincide well with the results presented by UV-vis spectrophotometry, in
addition to the results by XRD by calculating the size of the crystallite using the Debye-
Scherrer equation. It can be seen that the size of FeO NP is affected by the type of solvent
used for the extraction of metabolites from M. indica.

3.6. Characterization by Electron Energy Loss Spectroscopy (EELS)

The electronic structure of the FeO NP synthesized by the green route was analyzed.
For this, extensive EELS experiments were carried out. Figure 8 shows typical EELS spectra
for oxygen K edges and Fe-L2,3 edges for FeO NP 96% alcoholic extract and absolute
ethanolic extract. In both cases samples were collected from the central part. In Figure 8,
three peaks are shown (labeled A–C), where the loss of energy near the edge of the fine
structure can be identified in the K edge of oxygen; likewise, the intensities of the A peaks
are shown and B for FeO NP synthesized with absolute ethanolic extract are lower than
 Molecules 2021, 26, 7633 9 of 17

FeO NP with 96% alcohol. It has generally been shown that the intensities of the peaks
Molecules 2021, 26, x FOR PEER REVIEW 9 of 18
are attributed to oxygen vacancies within the nanostructures; therefore, the lower the
maximum intensity of the EELS spectra, the higher the content of oxygen vacancies in
FeO NP. Given this, it can be deduced that the vacant oxygen content is higher in FeO
diffractograms
NP synthesizedwhere there wasethanol
with absolute a peak extract
at 2θ atof26.2° attributable
M. indica to organic
than using stabilizing
the extract with
agents, in addition
96% alcohol. to the organic radicals shown in the FTIR.

Molecules 2021, 26, x FOR PEER REVIEW 10 of 18

Figure 7. TEM / STEM images
TEM/STEM images and
and size
size histogram
histogram of
of FeO
FeO NP
NP synthesized
synthesized using
using M.
M. indica
indica (a–d)
(a–d) with
with absolute
absolute ethanolic
ethanolic
extract and
extract and (e–h)
(e–h) with
with 96%
96% alcoholic
alcoholic extract.
extract.

The TEM image related to the FeO NP sample using 96% alcoholic solvent extract is
presented in Figure 7b, where spherical morphology is also evidenced with an average
size of 2.50 ± 0.47 nm.
The histogram shows the particle distribution and the mean size obtained. These di-
mensions coincide well with the results presented by UV-vis spectrophotometry, in addi-
tion to the results by XRD by calculating the size of the crystallite using the Debye-Scher-
rer equation. It can be seen that the size of FeO NP is affected by the type of solvent used
for the extraction of metabolites from M. indica.

3.6. Characterization by Electron Energy Loss Spectroscopy (EELS)

The electronic structure of the FeO NP synthesized by the green route was analyzed.
For this, extensive EELS experiments were carried out. Figure 8 shows typical EELS spec-
tra for oxygen K edges and Fe-𝐿 , edges for FeO NP 96% alcoholic extract and absolute
ethanolic extract. In both cases samples were collected from the central part. In Figure 8,
three peaks are shown (labeled A–C), where the loss of energy near the edge of the fine
structure can be identified in the K edge of oxygen; likewise, the intensities of the A peaks
are shown and B for FeO NP synthesized with absolute ethanolic extract are lower than
FeO NP with 96% alcohol. It has generally been shown that the intensities of the peaks are
attributed to oxygen vacancies within the nanostructures; therefore, the lower the maxi-
FigureFigure 8. EELS
8. EELS spectra
spectra of O-K
of O-K mumedges
edges (a)(a) and
intensity
and Fe-L
of
Fe-𝐿 the edgesspectra,
(b) acquired from
froma aFeO NPNP
96% alcoholic extract (red (red
curves)
, 2,3EELS
edges (b) the higher
acquired the content
FeO of
96% oxygen vacancies
alcoholic extract in FeO NP.
curves)
and FeO NP absolute ethanolic
and FeO NP absolute ethanolicGiven extract
extractthis,(blue
(blue curves),
it can respectively.
be deduced
curves), that the vacant oxygen content is higher in FeO NP synthe-
respectively.
sized with absolute ethanol extract of M. indica than using the extract with 96% alcohol.
Furthermore, the Fe-L edges provide us with the ionization state of the metal cations
by identifying the individual edges 𝐿 y 𝐿 , these results are shown in Figure 4. The gen-
eral results indicate the presence of 78% Fe and 22% O for FeO NP using absolute ethanolic
extract, while 52.03% Fe and 47.97% O for FeO NP using 96% alcohol extract.
Molecules 2021, 26, 7633 10 of 17

Furthermore, the Fe-L edges provide us with the ionization state of the metal cations
by identifying the individual edges L3 y L2 , these results are shown in Figure 4. The general
results indicate the presence of 78% Fe and 22% O for FeO NP using absolute ethanolic
extract, while 52.03% Fe and 47.97% O for FeO NP using 96% alcohol extract.

3.7. Characterization by Potential Zeta

The evaluation of the stability of the FeO NP was complemented by characterization
by zeta potential from its electrophoretic mobility. For this, 1 mM KCl saline solution was
used and adjusted to pH 6.5. The surface charge of the nanoparticles is considered an
important characteristic since it is closely related to the stability of the colloids [41]. This
is linked to the fact that it is a measure of the repulsion/electrostatic attraction between
particles, in addition to being a predictor of stability.
For FeO NP with extract in ethanolic solvent, the average values calculated were
34.13 ± 3.03 mV and electrophoretic mobility 2.67 ± 0.24 (µ/S/V/cm), while for NP with
extract in alcoholic solvent 96% the value was 22.01 ± 5.72 mV and electrophoretic mobility
1.72 ± 0.45 (µ/S/V/cm), which indicates high stability, and therefore lack of flocculation
due to aggregation. This is also corroborated in the characterization by UV-vis spectropho-
tometry (Figure 3).
It should be noted that colloids with a high zeta potential (−/+) are electrically
stable, whereas those with a low zeta potential (−/+) tend to coagulate [42]. Positive
values could indicate that there is no excess presence of functional groups from the extract
and some deprotonated biomolecules and therefore there is no coordination with the
nanostructures obtained.
The zeta potentials obtained are comparable to other research works related to green
synthesis [43,44].

3.8. Magnetization Measurements (SPION)

The magnetization curves are presented in Figure 9 (Ms vs. H). The results of both
Molecules 2021, 26, x FOR PEER REVIEW 11 of 18
FeO NP samples exhibit a behavior attributed to superparamagnetic materials typical of
SPIONS; in addition, the samples were evaluated at 5 and 300 K.

Figure 9.
Figure Measurements of
9. Measurements of saturation
saturation magnetization
magnetization versus
versus applied
applied field
field hysteresis
hysteresis for FeO NP
for FeO NP using
using extracts
extracts in
in ethanolic
ethanolic
and alcoholic solvents (a) 5 K, (b) 300 K.

For 55 K,
For K, aa maximum
maximumMs Mswas
wasobtained
obtainedaround
around20.5
20.5emu/g
emu/g and
and 6.13
6.13 emu/g.
emu/g. ThisThis
de-
decreased behavior was also evident when it was analyzed at 300 K, where
creased behavior was also evident when it was analyzed at 300 K, where values of 16.8values of 16.8
and 2.31
and 2.31 emu/g
emu/gwerewereobtained,
obtained,all
all of
of the
the aforementioned
aforementioned forfor the
the extracts
extracts in
in ethanolic
ethanolic and
and
alcoholic solvents respectively. In general, the magnetization values tend to decrease
when there is also a decrease in the diameter of the nanoparticle. This behavior is corrob-
orated in the results obtained by TEM/STEM and the size histogram with values of 3.18
and 2.50 nm for FeO NP using excerpts mentioned above.
The magnetic response values are lower compared to other methods such as thermal
 Molecules 2021, 26, 7633 11 of 17

alcoholic solvents respectively. In general, the magnetization values tend to decrease when
there is also a decrease in the diameter of the nanoparticle. This behavior is corroborated in
the results obtained by TEM/STEM and the size histogram with values of 3.18 and 2.50 nm
for FeO NP using excerpts mentioned above.
The magnetic response values are lower compared to other methods such as thermal
decomposition (76 emu/g) [45] and co-precipitation (60 emu/g) [46]. This reduction of Ms
is linked to a crystalline disorder, spin inclination due to the reduction of the coordination
of surface cations and/or negative surface effects promoted by a broken exchange between
spins in NP with small crystallite size [2,47]. Regarding other green synthesis methods,
Ms values lower than the one presented in this research have been reported (regardless
of the type of solvent used to obtain the extract), such as 23 emu/g [48], 5.35 emu/g [17],
7.78 emu/g [49], 11 emu/g [18], 0.015 emu/g [50], and 1.57 emu/g [51].
On the other hand, observed in Figure 10 is the curve of the magnetization as a function
of the temperature of the FeO NP obtained by the green route with the two types of extracts
mentioned. It can be seen that after cooling the sample under the influence of a magnetic
field, both have a different response when varying the temperature. In the case of the
sample with 96% alcoholic solvent extract, the increase in temperature generates a decrease
in the magnetization values for both the zero field cool measurements ZFC (orange) and
WFC (blue). This does not happen with the second sample, where it is evidenced that the
Molecules 2021, 26, x FOR PEER REVIEW
ZFC behavior increases until it reaches its maximum point of 3.09 emu/g. The response of
the WFC measure, by contrast, describes a decline. In both cases there is no evidence of
thermal instability.

Figure 10. Magnetization curve as a function of temperature at low fields, under the ZFC and WFC
Figure 10. Magnetization curve as a function of temperature at low fields, under the ZFC a
protocols (a) FeO NP Absolute ethanolic extract, (b) FeO NP 96◦ alcoholic extract.
protocols (a) FeO NP Absolute ethanolic extract, (b) FeO NP 96° alcoholic extract.
The green synthesis of nanoparticles is presented as a new and sustainable alternative
to replace
The other
green typical synthesis
synthesis of methods where inorganic
nanoparticles inputs are
is presented as used
a new throughout the
and sustainable
process, which raises production costs and contributes to the contamination of both nature
tive to replace other typical synthesis methods where inorganic inputs are used th
and the researchers who develop the methodology. However, in this type of ecological
out the process,
synthesis which
it is important to raises
have a production costsofand
good management the contributes to the
parameters linked to contamina
the
both nature
process, and
in order to the
haveresearchers
nanostructureswho develop
with the
similar or methodology.
better characteristicsHowever,
than those in this
developed by
ecological inorganic it
synthesis methods.
is important to have a good management of the parameters
to the process, in order to have nanostructures with similar or better characterist
those developed by inorganic methods.
In this sense, this research provides as a first alternative the use of agro-in
Molecules 2021, 26, 7633 12 of 17

In this sense, this research provides as a first alternative the use of agro-industrial
waste, specifically the peel of the mango fruit (M. indica), to extract the metabolites with
the potential to reduce metal salts (precursor). Thus, the influence of the type of solvent
used in the elaboration of the extract rich in bioactive compounds, such as absolute ethanol
and 96% alcohol, has been evaluated. This is also linked to a decrease in production costs.
To consider a correct synthesis of nanoparticles, it is necessary to carry out a complete
characterization that is evidenced from the analyses presented.
The results show a better result for the FeO NP synthesized using M. indica extract in
alcoholic solvent 96%. This is how the spectrophotometry practiced for the evaluation of
stability over time shows an invariance showing a slight increase in absorbance, possibly
due to which an incomplete reaction was generated, which motivated us to continue with
the reduction process and therefore resulted in a slight increase in the production of nanos-
tructures, which later became stable with the passage of time. The FTIR characterization
shows a possible mechanism involved in the reduction of the precursor agent (metal salt),
with the C=C and C=O groups being the ones that lead to soluble compounds that act as
reducing agents, such as flavonoids and terpenoids. It has been shown that the formation
of this type of nanomaterial has led to having FeO phases such as magnetite and with a
slight contribution of maghemite; likewise, the results of the elemental characterization
(EDS) show that this type of sample has Fe and O without no other type of element. The
morphology was evaluated by TEM/STEM, where the spherical type geometry is evi-
denced and with sizes close to the results obtained using the Debye-Scherrer equation from
the XRD diffractograms. The result for zeta potential reinforces the fact of having achieved
NP with high colloidal stability and the little participation of functional groups such as
traces from the extract.
A behavior of decrease in the maximum values of magnetization between both meth-
ods has been evidenced. This is related to the variation of the diameters of the nanos-
tructures, and because the magnetic properties are defined by characteristics such as size,
surface, and the crystalline structure; in this sense, by obtaining a lower value of magnetic
moment (emu/g) there is a possible alteration of the three-dimensional framework, moti-
vated by structural defects and size that give rise to different magnetization values [52].
In general, the FeO NP obtained reach the saturation state governed by the superparam-
agnetic nature, which makes it very feasible to respond to magnetic fields without delay,
indicating a material with high potential applicability in environmental remediation pos-
sess a perfect Langevin behavior that suggests the ability to act before an external magnetic
field without maintaining a residual magnetism when the same field is eliminated, which
further improves the various applications both in magnetic resonance imaging and cell
separation [53–55].
On the contrary, the FeO NP obtained using M. indica extract in absolute ethanolic
solvent show a high content of traces of organic material from the extract, since the
characterization by FTIR and reinforced with EDS show the presence of phosphorus and
calcium. It is also evident in the TEM/STEM images where there are very dense areas
specifically linked to the aforementioned elements; likewise, UV-vis results show greater
dynamics in the production of nanostructures with the passing of the days.
Thus, for the application in soil remediation, it has been considered to use FeO NP
with pure content of this material without the implication of another type of element, in
addition to considering smaller sizes and high monodispersity.
The agricultural soil used tests the influence of FeO NP in the removal of chromium
(Cr-VI), cadmium (Cd) and lead (Pb). The results obtained are presented in Table 1.
The removal of chromium (VI) with the 10 mL colloid (C2) obtained 99.48% removal
during a period of 30 min. In this way, a reduction from 734.07 ppm to 3.815 ppm was
achieved, which, compared to the Environmental Quality Standards (ECA) for agricultural
soil in Peru [56], exceeds 0.4 ppm. Our research, like other studies, has obtained an
efficient elimination of Cr (VI), and the formation of FeO nanoparticles and Fe (II) oxides
is attributed to being strongly reducing. This is based on its various properties such
Molecules 2021, 26, 7633 13 of 17

as the modifiability of the surface by substances and functional groups, as well as its
standard reduction potential, which for Fe2+/FeO is −0.44 V, being more negative than
for Cr 6+/Cr3+(+1.51 V) [44,57–59]. In addition, the redox reactions of ferrous and ferric
ions contribute to the process. The oxidation product binds pollutants through complex
formation and ion exchange; iron oxides serve as a flocculant to capture metal ions and,
therefore, remove contaminants present [60–62]. For the case of sample C1, there is no
evidence of variation in metal concentration even after treatment; similar results indicate
the decrease in removal due to the high initial concentration of Cr (VI) in the solution [63,64].
The effects between adsorbent dose and interaction time on chromium removal can prove
lack of removal in the indicated sample. Additionally, they point to Cr (III) as the main
responsible for forming a solid solution with iron, creating a passive layer of secondary
phases such as magnetite, green oxide, goethite, and ferric hydroxide. This is attributed
to the strong proton chemical gradient (Eh) that exists between the FeO surface and the
surrounding medium. Minerals with Fe in a lower oxidation state, such as magnetite
and green oxide, are often found close to FeO. The formation of such a passive layer
decreases the rate of Cr (VI) reduction in the iron plate [65]. Therefore, increasing the initial
concentration increases the degree of passivity and, therefore, decreases the reaction.

Table 1. Atomic absorption results in agricultural soil samples for chromium, cadmium, and lead; influence in function of
FeO NP.

CHROMIUM CADMIUM LEAD

Initial Final Removal Initial Final Removal Initial Final Removal
Sample Abs. Abs. Abs.
ppm ppm (%) ppm ppm (%) ppm ppm (%)
C3 0.0046 3.87 99.47 0.008 0.0465 81.48 0.16 467.91 5.90
C2 0.0045 734.07 3.815 99.48 0.0010 0.2511 0.1488 40.74 0.18 497.27 526.63 0
C1 1.17 734.07 0 0.013 0.3023 0 0.18 526.63 0

In the evaluation of the removal potential of cadmium, it presented a concentration

of 0.2511 ppm, a value that complies with the ECA regulations for soil (1.4 ppm). The C3
sample (15 mL of colloid) reached the maximum removal of 81.48%, which translates to a
concentration of 0.0465 ppm of cadmium in the analyzed test. Likewise, a proportional
relationship between the amount of colloid and the percentage of removal achieved is
evidenced, which means that as the milliliters of colloid in the sample decrease, the
concentration in ppm increases. Studies affirm that the amount of adsorbent is a critical
factor which determines the adsorption rate [66], thus there is a greater surface area of metal
ions when the adsorbent dose is increased. Finally, in a similar way, the presence of lead
was calculated and registered 497.27 ppm which decreased to 467.91 ppm, an approximate
of 30 ppm between the initial and final concentration because the pH is an influential
variable during the absorption of lead, it has been shown that pH < 4 protonation decreases
the amount of active sites causing an electrostatic repulsion condition on the surface of
the sorbent between H+ ions and Pb ions, causing less adsorption, likewise with pH > 6
it favors the generation of lead hydroxides which tend to precipitate [23,67]. A similar
situation is evidenced with Cadmium according to the literature, where a deprotonation
of the sample contributes to a better removal [68]. In our results, the high percentage of
removal of the Cadmium C3 sample is also due to the low initial concentration for metal
compared to Chromium and lead samples. However, the ideal pH situation for Chromium
is contrary to the other two metals because it needs a high degree of H+ ions to achieve good
removal efficiency. It has been shown that pH between 2 and 3 is usually the most suitable,
because metal ions can replace H+ ions adsorbed on the surface of iron oxide nanoparticles
through the ion exchange mechanism [69]. This can be explained by Equation (1) with the
reduction of Cr (VI) to Cr (III) by Fe2+ action of Fe3 O4 and subsequently coprecipitation in
hydroxides (Equation (2)) [13,70].
Molecules 2021, 26, 7633 14 of 17

HCrO4− + 3Fe2+ + 7H+ → 2Cr3+ + 3Fe3+ + 4H2 O (1)

(1 − x )Fe3+ + xCr3+ + 2H2 O → Crx Fe1− x (OH)3 + 3H+ (2)

In addition to the adsorption product of the electrostatic interaction of the pollutant
and the magnetic nanoparticles, products of the availability on the surface of the nanoma-
terial, other removal mechanisms have been presented, such as chemical diffusion between
adsorbent and adsorbate, surface precipitation, redox reactions, and ion exchange. In
addition to removing inorganic contaminants, iron oxides can act as flocculants for the
removal of colloidal organic substances in suspension [71]. We can mention the phytoreme-
diation process, where a study tried to improve from the fusion of nanotechnology and
photocatalytic degradation techniques to decontaminate soils. They obtained elimination
of Pb, Ni, and Cd within 45 days after the phytoremediation study [72]. Compared to the
method we used, the results were obtained in less time, which would be related to not
considering plant species in the treatment.

4. Conclusions
It was determined that the influence of the use on the type of solvent for the extrac-
tion of reducing metabolites from the M. indica shell is linked to the degree of alcohol
concentration, 96% being the one from which the most functional groups derived from
soluble compounds such as flavonoids and terpenoids have been extracted, in addition
to not affecting its properties. The FeO nanoparticles showed a spherical geometry with
sizes between 2.5 and 3.1 nm for FeO NP in alcoholic 96% and absolute ethanolic solvents
respectively. In addition, the XRD results confirm the presence of the magnetic phases
of the magnetite as a slight contribution of the maghemite phase. The EDX results show
that a maximum degree of alcohol concentration (absolute ethanol) generates the extrac-
tion of other elements (phosphorus and calcium) present in the extract and even in the
nanoparticles. The magnetic response exhibits in both cases a behavior attributed to super-
paramagnetic materials, indicating the ability to respond to magnetic fields without delay,
being a factor involved in the removal of metals. The successful synthesis of nanoparticles
was applied in the removal of metals, achieving maximum values of 99.48% for chromium,
81.48% cadmium, and 5.9% lead.

Author Contributions: Conceptualization, J.B.-G. and R.G.-M.; methodology, J.B.-G., R.G.-M., and
D.A.-C.; validation, D.A.-C.; formal analysis, J.B.-G., R.G.-M., and D.A.-C.; investigation, J.B.-G.
and R.G.-M.; resources, N.R.C. and D.A.-C.; data curation, N.R.C. and D.A.-C.; writing—original
draft preparation, J.B.-G. and R.G.-M.; writing—review and editing, D.A.-C.; visualization, D.A.-C.;
supervision, D.A.-C.; project administration, J.B.-G. and R.G.-M.; funding acquisition, J.B.-G. and
R.G.-M. 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: Not applicable.
Acknowledgments: The authors would like to thank LABNANO/CBPF for the technical support
during the electron microscopy work. Likewise, they thank the Dirección de Investigación e Inno-
vación of the Universidad Privada del Norte for their constant support and management.
Conflicts of Interest: The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.
Sample Availability: Samples of the compounds are not available from the authors.
Molecules 2021, 26, 7633 15 of 17

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