Silica-coated MgAl2O4 nanoparticles supported phosphotungstic acid as an effective catalyst for synthesis of α-aminophosphonates

Article abstract of DOI:10.1007/s11164-019-03737-z

In this research, a recoverable catalyst (MgAl₂O₄@SiO₂–PTA) was prepared by a simple utilization method. The prepared catalyst was characterized by XRD, FT-IR, SEM, EDX, ICP-AES, and BET techniques. The average crystallite size of MgAl₂O₄ was calculated to be 40?nm by the Debye–Scherrer formula. The nanocomposite was examined as a heterogeneous catalyst for synthesis of α-aminophosphonates under solvent-free conditions at room temperature. In this process, magnesium aluminate spinel (MgAl₂O₄), used as the base and supporting catalyst for H₃PW₁₂O₄₀ (PTA), provides the recycling and reusing of the catalyst and also increases the efficiency of the reaction, which is due to the increase in the surface/volume ratio. In order to obtain optimal conditions, the synthesis of α-aminophosphonates reactions was investigated with different solvents and catalysts. The results showed that α-aminophosphonate prepared from the benzaldehyde and aniline reaction has higher efficiency and a shorter time than other reactions. The catalyst was recovered by simple filtration, and it can be recycled for at least five successive times without loss of catalytic activity.

Full text of DOI:10.1007/s11164-019-03737-z

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03737-z
Silica‑coated MgAl2O4 nanoparticles supported
phosphotungstic acid as an efective catalyst for synthesis
of α‑aminophosphonates
Reza Hajavazzade1 · Ali Reza Mahjoub2 · M. Kargarrazi1
Received: 10 November 2018 / Accepted: 2 January 2019
© Springer Nature B.V. 2019
Abstract
In this research, a recoverable catalyst (MgAl2O4@SiO2–PTA) was prepared by a
simple utilization method. The prepared catalyst was characterized by XRD, FT-IR,
SEM, EDX, ICP-AES, and BET techniques. The average crystallite size of MgAl2O4
was calculated to be 40 nm by the Debye–Scherrer formula. The nanocomposite
was examined as a heterogeneous catalyst for synthesis of α-aminophosphonates
under solvent-free conditions at room temperature. In this process, magnesium alu-
minate spinel (MgAl2O4), used as the base and supporting catalyst for H3PW12O40
(PTA), provides the recycling and reusing of the catalyst and also increases the
efciency of the reaction, which is due to the increase in the surface/volume ratio.
In order to obtain optimal conditions, the synthesis of α-aminophosphonates reac-
tions was investigated with diferent solvents and catalysts. The results showed
that α-aminophosphonate prepared from the benzaldehyde and aniline reaction has
higher efciency and a shorter time than other reactions. The catalyst was recovered
by simple fltration, and it can be recycled for at least fve successive times without
loss of catalytic activity.
Keywords Catalyst · Nanocomposite · α-Aminophosphonates · Heterogeneous
catalyst · Solvent-free
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4-019-03737-z) contains supplementary material, which is available to authorized users.
*
Ali Reza Mahjoub
mahjouba@modares.ac.ir
1
2
Department of Chemistry, Tehran North Branch, Islamic Azad University, Tehran, Iran
Department of Chemistry, Faculty of Science, Tarbiat Modares University,
P.O. Box 14155-4838, Tehran, Iran
Vol.:(0123456789)
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R. Hajavazzade et al.
Introduction
The choice of an efective modifcation on a catalyst can be improved by the selec-
tivity, activity, and recycling properties. Recently, nanoparticles have attracted
interest as solid supports for homogeneous catalysts immobilization [1, 2]. The
nanoparticles can provide suitable media to access the substrate molecules due to
the high surface-volume ratio. Meanwhile, it can be isolated efciently from the
product solution after completing the reactions [3, 4].
Polyoxometalates are a category of inorganic metal-oxide cluster group that
can receive one or more electrons to yield species with mixed valence. Heter-
opolyacid (HPAs) catalysts have attracted considerable attention in industrial and
academic felds due to their unique properties. Among various HPAs, hetropo-
lyacid compounds of the Keggin structure have gained extensive applications,
due to their strong activity, good catalytic properties, suitable redox sites, and
selectivity for special reaction products [5–13]. Polyoxometalates have two major
limitations: low surface area (< 10 m2 g−1) and solubility in polar solvents. These
two interfere with the reaction efciency and restrict the reusability of the cata-
lysts. Most of the acidic protons are inaccessible for catalysts in nonpolar hydro-
carbon reactions in bulk phosphotungestic acid. Supporting on nanoparticles is
the main solution for improving the efective surface and solubility in polar sol-
vents [14–17]. Mesoporous type materials such as silica, zeolites, alumina, zir-
conia, and, titania have been used as support for PTA [18–22]. Silica (SiO2) is a
typical mesoporous material and it has also attracted growing interest in diverse
applications due to its chemical and physical stability, good biocompatibility and
hydrophilic nature [23, 24]. The tedious recovery method via fltration and the
indispensable loss of the solid catalyst in the separation process still limits its
application, especially for the small nano-sized particles, while PTA supported
on silica shows high catalytic efciency and can be recycled more readily than its
homogeneous counterpart method.
Magnesium aluminate (MgAl2O4) is one of the most important catalysts with
much heat resistance and chemical and structural stability. It has various applica-
tions in humidity sensors, ceramic capacitors, fusion reactors, and catalysts [25,
26]. Magnesium aluminate has a low density (3.58 g/cm3), high melting point
(2135 °C), and good resistance against chemical attacks as well as very high
temperatures [27]. Diferent methods for synthesis of spinel magnesium alumi-
nate with particular characteristics, high purity, and low particle size have been
reported, such as co-precipitation [28] of ions in solution, sol–gel [29, 30], micro-
wave [31], solution combustion and solid state [32, 33]. Selecting the method
depends on the chemical homogeneity of magnesium aluminate. These processes
are mostly expensive or the environment limits them in large scale production.
In general, smaller particle size with a higher surface area is suitable for vari-
ous catalytic applications [34]. There were several types of research reported on
silica-based composite materials and their applications [35–39].
In this study, a novel method is reported for immobilization of (PTA) silica
coated magnesium aluminate nanoparticles. This nanocomposite was used as a
1 3

Silica‑coated MgAl2O4 nanoparticles supported…
catalyst for the preparation of α-aminophosphonates under solvent-free condi-
tions at room temperature. In the recent few decades, α-aminophosphonates have
been prepared using various methods and catalysts [40–42], (see Scheme 1).
Experimental
Materials and methods
All chemicals were purchased from Sigma-Aldrich or Merck with analytical grade
and used as received. H3PW12O40 (PTA) was purchased from Sigma-Aldrich. Fou-
rier transform infrared (FT-IR) spectra were obtained using a FT BOMEM MB102
IR spectrophotometer. X-ray difraction (XRD) patterns of the synthesized samples
were recovered with a Philips X-ray difractometer (model PW1730) The SEM and
EDX images were obtained by a Hitachi Scanning Electron Microscope.
Synthesis of MgAl2O4@SiO2–PTA nanocomposite
MgAl2O4 was prepared using the method reported by Mostafa Y. Nassar, with some
minor modifcation [43]. To a coating of MgAl2O4 nanoparticles with a layer of sil-
ica, ethanol (1.5 ml), and, H2O (10 ml) were mixed in a fask and were placed in an
ultrasonic bath for 1 h. After that, NH3 (1.5 ml) was added to this mixture. Then 2 g
of MgAl2O4 particles were dispersed in it, and the mixture was vigorously stirred at
40 °C for 10 min. Then TEOS (0.53 ml) was added dropwise and mixing was con-
tinued for 1 h, and the mixture was stirred overnight. The coated particles were sep-
arated by fltration and washed with ethanol several times and dried at 80 °C in an
oven. In this method for preparation of nanocomposite, ethanol/water (80:20 ratio)
solution containing 1.0 g of PTA was mixed together, and the solution was stirred at
room temperature for 1 h. Then, 1.0 g of MgAl2O4@SiO2 was dispersed and stirred
for an additional 3 h at the same temperature. The resulting solid was separated by
fltration, and lastly, this nanocomposite was washed with absolute ethanol and dried
in an oven at 100 °C for 2 h. The amount of PTA in MgAl2O4@SiO2–PTA nano-
composite was determined by ICP-AES analysis to be 0.087 mmol g−1. The typical
preparation of composite (MgAl2O4@SiO2–PTA) is shown in Scheme 2.
O
O
P
O
O
NH2
+
O
+
catalyst
O
P
O
HN
solvent free
Scheme 1 MgAl2O4@SiO2–PTA catalyzed synthesis of α-aminophosphonates
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R. Hajavazzade et al.
Scheme 2 Typical preparation procedure of the synthesis of MgAl2O4@SiO2–PTA nanocomposite
General procedure of catalytic α‑aminophosphonates synthesis
A mixture of aniline (1 mmol), aldehyde (1 mmol), triethyl phosphite (1.2 mmol)
and MgAl2O4@SiO2–PTA catalyst (0.05 g) was stirred at room temperature. The
reaction was being monitored by TLC. Chloroform was added to dilute the reac-
tion mixture, and the organic layer was simply isolated by fltration, at the end
of the reaction. The isolated solution was purifed on a silica-gel plate to obtain
the pure product. The identities of the products were confrmed by FT-IR and
1HNMR spectral data.
Results and discussion
Characterization of MgAl2O4@SiO2–PTA composite
FT‑IR spectra
MgAl2O4@SiO2–PTA nanocomposite was manufactured via a simple procedure.
MgAl2O4 was prepared by the sol–gel combustion method as a support for nano-
composite, then it was coated by a thin layer of silica. The synthesized nano-
composite was characterized by diferent techniques. The FT-IR spectra of all
synthesized samples along with the pure PTA are presented in Fig. 1. In the IR
spectra, the MgAl2O4 samples displayed two vibrations stretching at 555 cm−1
and 700 cm−1 consecrated to the [AlO6] groups, the lattice vibration of Mg–O
stretching, and displaying the formation of MgAl2O4 spinel [44, 45]. Two vibra-
tional bands at 3438 cm−1 and 1631 cm−1 appeared in the IR spectra of the
products that could be attributed to the stretching and bending vibrations of the
adsorbed surface molecular water interacting with MgAl2O4 [46–49]. Two bands
were observed at 1063 cm−1 and 809 cm−1 which are ascribed to the symmetri-
cal and asymmetrical vibrations of the Si–O–Si bonds. Two bands at 894 cm−1
1 3

Silica‑coated MgAl2O4 nanoparticles supported…
Fig. 1 FT-IR spectra of MgAl2O4 (a), MgAl2O4@SiO2 (b) and MgAl2O4@SiO2–PTA (c)
and 981 cm−1 are observed in the spectrum of MgAl2O4@SiO2–PTA, which are
respectively imputed to the W–O–W and W=O stretching modes of PTA [50, 51].
X‑ray difraction
The XRD patterns of MgAl2O4, MgAl2O4@SiO2, MgAl2O4@SiO2–PTA, are dis-
played in Fig. 2. The difraction peaks related to Bragg’s refections from (111),
(220), (311), (400), (422), (511), (440), and (533) planes corresponded to the stand-
ard spinel structure of MgAl2O4 (JCPDS Card No. 01-075-1798) (see Fig. 2a). The
average crystallite size of MgAl2O4 nanoparticles was about 40 nm, as determined
1 3

R. Hajavazzade et al.
Fig. 2 XRD patterns of MgAl2O4 (a), MgAl2O4@SiO2 (b), MgAl2O4@SiO2–PTA(c)
using the Debye–Scherrer formula. The XRD patterns of MgAl2O4, after coating
with silica and solitary with PTA are shown in Fig. 2b, c, which are more or less
similar to the previous MgAl2O4 with the spinel structure.
Scanning electron microscopy (SEM)
The morphology of the samples was investigated by SEM. The SEM images of
MgAl2O4, MgAl2O4@SiO2 and MgAl2O4@SiO2–PTA are presented in Fig. 3. SEM
images display that MgAl2O4, MgAl2O4@SiO2, and MgAl2O4@SiO2–PTA particles
are well dispersed and most of the prepared nanoparticles have spherical structure
(Fig. 3a–c).
EDX microscopy and Brunauer–Emmett–Teller (BET) surface area analysis
The EDX spectrum is shown in Fig. 4. This spectrum obviously reveals the pres-
ence of all the expected main elements (O, Si, P, Al, Mg, and W) including the three
mentioned component composites. The surface area of MgAl2O4@SiO2–PTA was
also estimated using the N2 gas adsorption (BET) method and a value of 36.73 m2
g−1, average pore diameter is about: 15.00 nm and total pore volume: 0.1463 cm3
g−1 were obtained for this composite. The graph of nitrogen adsorption–desorption
isotherm of the MgAl2O4@SiO2–PTA is presented in Fig. 5.
1 3

Silica‑coated MgAl2O4 nanoparticles supported…
Fig. 3 SEM image of MgAl2O4 (a), MgAl2O4@SiO2 (b), MgAl2O4@SiO2–PTA(c)
α‑Aminophosphonates synthesis
To optimize the reaction conditions of α-aminophosphonates synthesis, diferent
portions were accomplished at room temperature by using aniline, benzaldehyde and
triethyl phosphite as substrates in the presence of MgAl2O4@SiO2–PTA as a cata-
lyst. In order to obtain the best media, the various solvents such as H2O, CH3CN,
C2H5OH, THF, DMF, Toluene, CH2Cl2, and solvent-free conditions were consid-
ered. The results are listed in Table 1. Much better results were received when this
reaction was done with the solvent-free conditions (see Table 1).
MgAl2O4, MgAl2O4@SiO2, H3PW12O40, H2SO4, SiO2@Al2O3, CuI, and in addi-
tion to MgAl2O4@SiO2–PTA as catalysts studied, in order to obtain the efectiveness
1 3

R. Hajavazzade et al.
Fig. 4 EDX spectrum of MgAl2O4@SiO2–PTA nanocomposite
Adsorpꢀon / desorpꢀon isotherm
120
80
40
0
0
0.5
1
p/p0
ADS
DES
Fig. 5 Graph of nitrogen adsorption–desorption isotherm of the MgAl2O4@SiO2–PTA
of PTA species on this catalytic reaction. As indicated in Table 2, MgAl2O4@
SiO2–PTA showed the best catalytic activity for the α-aminophosphates synthesis.
The highest yield received was for aniline and benzaldehyde reaction.
The given results in Table 3 show that the condensations procedures were com-
pleted within 5–55 min, with good isolated yields with MgAl2O4@SiO2–PTA used
as a catalyst. The α-aminophosphonates syntheses have been reported in diferent
methods [52–56]. These methods have been used under certain circumstances such
as long reaction time, toxic catalysts, the presence of solvents and high temperature.
1 3

Silica‑coated MgAl2O4 nanoparticles supported…
Table 1 Efect of various
Entry
Solvent
Time
Yield (%)a
solvents on the synthesis of
α-aminophosphonates
1
H2O
50 min
30 min
45 min
5 min
5 h
10 h
8 h
30 min
80
75
72
97
70
59
75
82
2
3
4
5
6
7
8
CH3CN
C2H5OH
Solvent free
THF
DMF
Toluene
CH2Cl2
All reaction conditions: benzaldehyde (1 mmol), aniline (1 mmol)
P(OEt)3 (1.2 mmol), catalyst (0.05 g) at room temperature
aIsolated yields
Table 2 Efect of various
catalysts on the synthesis of
α-aminophosphonates
Entry
Catalyst
Time (min)
Yield (%)a
1
2
3
4
5
6
7
MgAl2O4
120
120
5
10
45
50
300
–
–
MgAl2O4@SiO2
MgAl2O4@SiO2–PTA
H3PW12O40
H2SO4
SiO2@Al2O3
CuI
97
89
60
85
84
All reaction conditions: benzaldehyde (1 mmol), aniline (1 mmol),
P(OEt)3 (1.2 mmol), catalyst (0.05 g) at room temperature and sol-
vent free
aIsolated yields
Since high yields of α-aminophosphates were obtained in solvent-free condi-
tions and in a short reaction time at room temperature, these catalyst synthesis of
α-aminophosphates can signifcantly reduce drawbacks. On the other hand, this cat-
alyst can be separated from the reaction product by fltration and is recyclable sev-
eral times with no noticeable loss in its activity.
Spectra data
Die1thyl phenyl (phenyl amino) methyl phosphonate (Table 3, product of Entry
1) HNMR (500MHZ, CDCl3): ꢀ 1.12–1.15 (t, 3H, CH3), 1.29–1.32 (t, 3H, CH3),
3.63–3.71 (m, 1H, CH2), 3.90–3.97 (m, 1H, CH2), 4.05–4.17 (m, 2H, CH2), 4.74
(S, 1H), 4.79 (S, 1H), 6.58–6.60 (d, J=10HZ, 3H), 6.68 (S, 1H), 6.69–6.71 (d,
J=10HZ, 1H), 7.09 (S, 1H), 7.10–7.12 (d, J=10HZ, 2H), 7.25 (S, 1H), 7.28 (S,
1H), 7.32 (S, 1H), 7.33–7.35 (d, J=10HZ, 2H), 7.46–7.48 (d, J=10HZ, 3H). IR
1 3

R. Hajavazzade et al.
Table 3 Synthesis of diversifed α-aminophosphonates in the presence of MgAl2O4@SiO2–PTA
O
NH2
H
79
84
95
8
55
55
20
C l
OMe
O
NH2
H
9
Cl
Me
O
NH2
H
10
11
OMe
O
NH2
H
20
95
83
95
-
OMe
NH2
Me
O
H
40
35
12
13
OMe
NH2
OMe
O
O
H
OMe
OMe
NH2
a
H
120
14
aBenzaldehyde (1 mmol), aniline (1 mmol), P(OEt)3 (1.2 mmol), without catalyst at room tempera-
ture. All reaction condition: aldehydes (1 mmol), amine (1 mmol), P(OEt)3 (1.2 mmol) and (0.05 g) of
MgAl2O4@SiO2–PTA at room temperature
bIsolated yields
1 3

Silica‑coated MgAl2O4 nanoparticles supported…
(KBr) ʋmax/cm−1: 3294, 3048, 3029, 2982, 2934, 2908, 1605, 1525, 1497, 1454,
1391, 1365, 1273, 1236, 1058, 1017, 953, 798, 751, 734, 694, 572, 557.
Diethyl p1henyl (phenyl amino) (m‑tolyl) methyl phosphonate (Table 3, product of
Entry 2) HNMR (500 MHZ, CDCl3): ꢀ 1.12–1.14 (t, 3H, CH3), 1.27–1.30 (t, 3H,
CH3), 3.66–3.74 (m, 1H, CH2), 3.78 (S, 3H), 3.91–3.99 (m, 1H, CH2), 4.05–4.17
(m, 2H, CH2), 4.70 (S, 1H), 4.75 (S, 1H), 6.58–6.60 (d, J=10 HZ, 2H), 6.68–6.70
(t, J=10 HZ, 1H), 6.79–6.81 (d, J=10 HZ, 1H), 7.01 (S, 1H), 7.05 (S, 1H), 7.06
(S, 1H), 7.08–7.12 (t, J=10 HZ, 2H), 7.22–7.25 (t, 1H). IR (KBr) ʋmax/cm−1: 3301,
3033, 2979, 2904, 1601, 1530, 1497, 1466, 1439, 1387, 1365, 1250, 1030, 972, 869,
787, 745, 694, 600, 572.
Diethyl p1henyl (phenyl amino) (O‑ethyl) methyl phosphonate (Table 3, product of
Entry 5) HNMR (500 MHZ, CDCl3): ꢀ 1.04–1.07 (t, 3H, CH3), 1.32–1.34 (t, 3H,
CH3), 3.59–3.67 (m, 1H, CH2), 3.88–3.94 (m, 1H, CH2), 3.69 (S, 3H), 4.16–4.23
(m, 1H, CH2), 5.39 (S, 1H), 5.44 (S, 1H), 6.62–6.64 (d, J=10 HZ, 2H), 6.67–6.70 (t,
J=10HZ, 1H), 6.90–6.94 (t, J=10 HZ, 1H), 6.95 (S, 1H), 7.10 (S, 1H), 7.11–7.13
(d, J=10 HZ, 1H), 7.23–7.25 (d, J=10 HZ, 1H), 7.26 (S, 1H), 7.47–7.49 (d, J=10
HZ, 1H). IR (KBr) ʋmax/cm−1: 3295, 3105, 3033, 2982, 2908, 2873, 1604, 1518,
1497, 1460, 1439, 1391, 1366, 1316, 1279, 1246, 1229, 1091, 1056, 1023, 969, 886,
796, 773, 747, 693, 583, 510.
Diethyl (2‑methoxy phenyl amino) (P‑tolyl) methyl phosphonate (Table 3, product
1
of Entry 11) HNMR (500 MHZ, CDCl3): ꢀ 0.88–0.94 (m, 1H), 1.14–1.17 (t, 3H,
CH3), 1.25–1.28 (t, 3H, CH3), 2.3 (S, 3H), 3.69–3.80 (m, 1H, CH2), 3.87 (S,3H),
3.94–4.04 (m, 1H, CH2), 4.048–4.14 (m, 2H, CH2), 4.70 (S, 1H), 4.75 (S, 1H), 6.40
(d, 1H), 6.42 (d, 1H), 6.62 (t, 1H), 6.65 (t, 1H), 6.68 (t, J=10 HZ, 1H), 6.71 (t,
J=10 HZ, 1H), 6.74 (d, 1H), 6.76 (d, 1H), 7.11 (S, 1H), 7.12 (S, 1H), 7.26 (S, 3H),
7.33 (d, J=10 HZ, 1H), 7.35 (d, 1H). IR (KBr) ʋmax/cm−1: 3422, 2982, 2932, 2835,
1601, 1511, 1456, 1431, 1391, 1367, 1244, 1050, 1023, 967, 833, 783, 740.
Recycling of the catalyst
The reusability of the catalysts is a major priority and has to be performed in
heterogeneous methods. Recycling the MgAl2O4@SiO2–PTA catalyst in this
process can be performed in the same method as the tested one under the opti-
mized conditions. The catalyst was gathered by fltering, followed by washing it
twice with ethanol. Then it was dried at 100 ◦C for 2 h, after that, it was reused
in a new reaction. The results are presented in Table 4. The recovered catalyst
could be reused for fve successive times without any changes in the activity (see
Table 4). The FT-IR spectrum of the recovered catalyst showed no changes after
it has been used for fve successive times (see Fig. 6).
1 3

R. Hajavazzade et al.
Table 4 Reusability of
MgAl2O4@SiO2–PTA catalyst
in the model reaction
Entry
Time (min)
Yield (%)a
Fresh
5
5
5
5
5
5
97
96
94
93
92
91
1
2
3
4
5
All reaction conditions: benzaldehyde (1 mmol), aniline (1 mmol),
P(OEt)3 (1.2 mmol), MgAl2O4@SiO2–PTA as catalyst (0.05 g) at
room temperature and solvent free
aIsolated yields
Fig. 6 FT-IR spectra of catalyst: recycled catalyst after fve runs
Proposed mechanism for synthesis of α‑aminophosphonates
Scheme
3 represents the proposed mechanism for the preparation of
α-aminophosphonates. This reaction is likely to be accelerated by the phospho-
nate activated imine. As indicated in the Scheme 3, in this reaction, the phospho-
nium intermediate is formed by the nucleophilic addition of triethyl phosphite
to the imine, then it reacts with the water produced from the imine formation
phase, and forms α-aminophosphonate and ethanol [57] (see Scheme 3).
1 3

Silica‑coated MgAl2O4 nanoparticles supported…
MgAl2O4@SiO2-H2PW12O40
MgAl2O4@SiO2-H2PW12O40
H
H
Ph
O
NH2
N
H
H
+
P(OEt)3
-H2O
+
H2O
Ph
Ph
NH
NH
EtOH
OH
P(OEt)2
O
P
EtO
O
Et
EtO
Scheme 3 Proposed mechanism for synthesis of α-aminophosphonates
Conclusions
In this research, fabrication of a novel nanocomposite as a catalyst using MgAl2O4
nanoparticles as support via a simple procedure was studied. The synthesized cata-
lyst was considered by XRD, FT-IR, SEM, EDX, ICP-AES, and BET techniques.
This catalyst was used in some α-aminophosphates reactions under solvent-free con-
ditions, at room temperature in short reaction times. This nanocomposite reaction
was carried out under solvent free conditions, that can be considered as a “green
procedure”. The immobilized PTA catalyst could be recovered by simple fltration
and reused at least fve times without signifcant loss of activity.
Acknowledgements Financial support of this paper by Tehran North Branch, Islamic Azad University,
and Tarbiat Modares University, is thankfully acknowledged. Also acknowledged is Reza Hajavazzade,
Ph.D. student who did all the experiments, Alireza Mahjoub, Supervisor of the project, and Maryam Kar-
gar Razi, Advisor of the project.
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