Magnetic Fe–Cr–Ni oxide alloy nano-belts prepared from the chemical decomposition of a stainless steel screw (a top-down approach): an efficient and cheap catalyst for multicomponent reactions

Article abstract of DOI:10.1007/s13738-019-01814-z

Abstract: A new, cheap, and accessible method has been used for the preparation of nano-belts from the chemical decomposition (top-down approach) of a cheap stainless steel screw and found as an efficient magnetically recyclable nanocatalyst for the prepa

Full text of DOI:10.1007/s13738-019-01814-z

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-019-01814-z
ORIGINAL PAPER
Magnetic Fe–Cr–Ni oxide alloy nano‑belts prepared from the chemical
decomposition of a stainless steel screw (a top‑down approach):
an efcient and cheap catalyst for multicomponent reactions
Milad Kazemnejadi1 · Zeinab Sharaf2 · Boshra Mahmoudi3 · Atefeh Zeinali1 · Mohammad Ali Nasseri1
Received: 21 August 2019 / Accepted: 11 November 2019
© Iranian Chemical Society 2019
Abstract
A new, cheap, and accessible method has been used for the preparation of nano-belts from the chemical decomposition
(top-down approach) of a cheap stainless steel screw and found as an efcient magnetically recyclable nanocatalyst for the
preparation of quinolines and 1,8-dioxo-octahydroxanthenes under mild reaction conditions. The nano-belts, Fe–Cr–Ni
oxide alloy, was prepared in a two-step synthesis and characterized with various instrumental methods. Due to magnetic
property of the screw (a ferritic-alloy), the resultant nano-belts is magnetic. Magnetic Fe–Cr–Ni alloy nano-belts were
applied toward efcient preparation of quinolines and 1,8-dioxo-octahydroxanthenes under mild conditions. The catalyst
could be readily recovered and recycled for several consecutive runs, while it sufers from a very low metal leaching and
subsequently efciency drop.
Graphic abstract
Keywords Fe–Cr–Ni-Mo alloy · Intrinsic magnetic · Xanthene · Quinoline · Stainless steel screw precursor
Introduction
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s13738-019-01814-z) contains
The top-down method is one of the most applicable strategies
supplementary material, which is available to authorized users.
for the preparation of nanoparticles [1], frst introduced by
Feynman [1, 2] as a method for making particles in nanom-
eter dimensions. In this method, nanoparticles are produced
from larger masses of materials using shaving, milling, etc.
* Milad Kazemnejadi
miladkazemnejadi@birjand.ac.ir
Extended author information available on the last page of the article
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
Mechanical alloying, nanolithography, and severe plastic
deformation are three main top-down approaches for the
preparation of NPs [3, 4]. However, they involve harsh reac-
tion conditions and need expensive process (instruments,
solvents, time, etc.). In this study, we are going to intro-
duce another top-down approach for the synthesis of metal
alloy nanoparticles from an oxidizing mixture solution of
HNO3/DMSO/NaOCl (HDN reagent). The present method
is cheap and easy handling, which produces nanoparticles
in two steps. Screw was chosen as a bulk precursor for the
synthesis of NPs that was subjected to these solutions, and
the prepared nano-belts were used as an efcient magnetic
nanocatalyst for organic reactions.
alkyl or aryl aldehydes [23] in acidic conditions. Among
them, multicomponent domino Knoevenagel–Michael reac-
tion of two equivalents of 1,3-cyclohexadione with alde-
hydes [6] is the most current approach for the synthesis
of xanthenes in the presence of various types of catalysts
such as: Lewis acids [20], ZrO2 [24], SmCl3 [25], Fe3O4@
SiO2-HPW (HPW = phosphotungstic acid) [26], tetrapro-
pylammonium bromide (TPAB) [27], silica sulfuric acid
[19], sulfonated starch nanoparticles [28], ultrasound [29],
Fe3O4@SiO2@GMSI-VB1-Ni2+ (GMSI = (3-glycidyloxy-
propyl) trimethoxysilane; VB1=covalent bonding of thia-
mine [17], CuS quantum dots [30], sulfated polyborate [31],
nano-TiO2 [32], Fe3O4@SiO2–SO3H [33], and N-sulfonated
DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane) [34].
Very recently, Kim and co-workers reported the catalyst-
free synthesis of xanthenes in a water–ethanol medium [18].
Despite considerable progress in synthesis of quinolines
and 1,8-dioxo-octahydroxanthenes, they sufer from numer-
ous drawbacks including low yields, tedious work-up, long
reaction times, use of expensive and toxic reagents, and are
not environmentally friendly.
Heterocyclic compounds received considerable atten-
tion due to various biological and chemical applications
[5, 6]. Quinolines and xanthenes are two main classes of
heterocycle chemistry. Quinolines constitute a most appli-
cable class of N-containing heterocyclic compounds that
have been caught attention of researchers due to of their
broad range of biological activities such as antimicrobial,
anti-infammatory, antihypertensive, anti-asthmatic, anti-
cancer, and antimalarial [7]. Quinolines can be found in
natural products (especially in alkaloids), shale oil, petro-
leum, wood preservation, and coal processing [8]. Various
methodologies have been developed for the preparation of
quinolines for sake of their inevitable applications in biolog-
ical and organic synthesis such as: Combes, Pftzinger, Con-
rad–Limpach, Skraup, Doebner–von Miller, and Friedländer
annulation. Friedländer annulation is the most popular and
straightforward approach for the preparation of quinolines
that involves condensation cyclization between an active car-
bonyl compound containing an active α-methylene group
and 2-aminoaryl ketones [9]. The reaction could be cata-
lyzed by a variety of acid-based catalysts or transition metal-
based catalytic systems that can be point to some recently:
(1) microwave [10], (2) malic acid [11], (3) [MoO2]2+ [12],
(4) [Mn(CO)5Br] [5], (5) α-Chymotrypsin [7], (6) sulfonyl
imidazolium salt [13], (7) Fe3O4@SiO2@ZnCl2 [14], (8)
benzylamine [8], (9) carbon aerogel [15], and (10) calcium
silicate nanoparticles [16].
Herein, in accordance with green chemistry considera-
tion as well as economical and industrial aspects, we have
reported a cheap magnetic nanocatalyst Fe–Cr–Ni oxide
alloy that is prepared by the chemical decomposition of a
stainless steel screw with easily accessible and high catalytic
activity for the construction of quinoline as well as xanthene
derivatives in water as a green solvent at room temperature.
Experimental
Materials and instrumentation
A carbon alloy of screw (ferritic stainless steel 304) with
25 mm height, 4.0 mm width, 2.223 g, was purchased
from PICHSASAN ARAS IRANIAN Co., and used for
the chemical decomposition and subsequently catalyst
preparation. All solvents and reagents were in analytical
grade and provided from Sigma and Fluka companies.
Reactions progress was monitored by thin layer chro-
matography (TLC). FTIR spectra were recorded using a
JASCO FT/IR 4600 spectrophotometer using KBr pellet.
Xanthene is another important class of heterocyclic com-
pounds that contains the pyran ring. Numerous biological
activities have been known for them such as anti-bacterial,
anti-infammatory, anti-viral, photodynamic therapy, anti-
plasmodia, and laser technology [6, 17, 18]. Also, they
played a vital role in other felds of science such as agricul-
tural, industrial, material science, and medicinal chemistry
[19, 20]. Xanthene ring can be constructed via various meth-
ods including: (1) Knoevenagel–Michael reaction of two
equivalents of 1,3-cyclohexadione with aldehydes (2) cyclo-
condensation reaction of 2-hydroxyaromatic aldehydes and
2-tetralone [21], (3) the reaction of benzaldehyde and ace-
tophenone [22], and (4) the condensation of β-naphthol with
1
The H NMR and 13CNMR spectra were recorded on a
Bruker AVANCE III 300 MHz spectrometer in CDCl3 and
DMSO-d6 as a solvent and TMS as an internal standard.
Field emission scanning electron microscopy (FE-SEM)
images were obtained on a FEI NOVA NanoSEM 450.
EDX spectroscopy was performed using field emission
scanning electron microscope (FE-SEM, JEOL 7600F),
equipped with a spectrometer of energy dispersion of
X-ray from Oxford instruments. XPS studies were con-
ducted using an XR3E2 (VG Microtech) twin anode X-ray
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Journal of the Iranian Chemical Society
source with Al Kα = 1486.6 eV. Transmission electron
microscopy (TEM) was performed on a Philips EM208
microscope and was operated at 100 kV. DLS analysis
for the nano-belts was performed on a HORIBA-LB550
instrument. The data were analyzed by DTS applica-
tions 5.10 software. The detection angle was 90 °C for
the size measurement, and the intensity average particle
size of the nano-belts was measured by a nonnegative
least squares analysis method [35]. TGA of the samples
has been performed on a NETZSCH STA 409 PC/PG in
nitrogen atmosphere with a heating rate of 10 °C/min
in the temperature range of 25–1000 °C. The magnetic
behavior of the samples was conducted on Lake Shore
vibrating sample magnetometer (VSM) at room tempera-
ture. The surface area, pore volume, and pore diameter
of the obtained NPs were determined by N2 physisorp-
tion at − 196 °C with surface area and pore size analyzer
(Micromeritics ASAP 2000 instrument) using the BET
method. Metal leaching studies were performed using an
inductively coupled plasma mass spectrometer (ICP-MS)
Thermo Elemental VG PQ ExCell. XRF analysis was car-
ried out by a XRF Philips PW1730 instrument. The sur-
face area, pore volume, and pore diameter of the obtained
NPs were determined by N2 physisorption at − 196 °C
with surface area and pore size analyzer (Micromeritics
ASAP 2000 instrument) using the BET method.
Preparation of the catalyst
In a 100 mL beaker, a ferritic stainless steel-304 with
2.223 g in weight was placed and 5 mL DMSO and 5 mL
NaOCl solution were added (Fig. 1). Then, 10 mL HNO3
65% was added to the solution. Immediately after the addi-
tion, a red color of NO2 gas was generated and chemical
decomposition/corrosion of the screw was started. The
temperature remained constant at 75 °C during decomposi-
tion, so that the boiling solution was quite clear (no external
heating was applied). The decomposition continued to com-
plete dissolution of the screw, and a transparent dark brown
solution was obtained (no suspensions or gels are formed).
The complete dissolution takes 35 min. The resultant solu-
tion was centrifuged to eliminate any unreacted metal screw.
Then, the solution was neutralized with NaOH 1 N. Upon
neutralization, the dark brown sediment was obtained. The
precipitate was washed several times with deionized water
(2×20 mL) and EtOH (2×20 mL), dried into oven (60 °C),
and isolated as a stable powder at room temperature in air
atmosphere. An experimental view for the preparation of the
catalyst is shown in Fig. 1.
Typical procedure for preparation
of 1,8‑dioxo‑octahydroxanthenes
To a 25 mL round bottom fask, benzaldehyde (1.0 mmol)
and dimedone (2.2 mmol) were added to 2 mL of water.
Fig. 1 An experimental sche-
matic for the preparation of
the magnetic Fe–Cr–Ni alloy
nanoparticles
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Journal of the Iranian Chemical Society
The catalyst (5 mg) was added to the mixture, and the
resulting mixture was stirred for the appropriate time at
room temperature. The reaction progress was monitored by
TLC. Upon reaction completion, 5 mL ethanol was added
to the mixture and the catalyst was separated by an exter-
nal magnetic feld. Then, the product was extracted with
EtOAc (3 × 7 mL). The organic phases were combined,
and the solvent was removed under reduced pressure. The
crude product was recrystallized from EtOH to aford the
pure xanthene product.
Results and discussion
Catalyst characterization
The prepared nano-belts were characterized by various
spectroscopic methods. FTIR spectrum represents a series
of peaks at 444–681 cm−1 that could be assigned to Fe–O,
Cr–O or Ni–O stretching vibrations [36, 37]. This is com-
pletely in agreement with magnetic behavior of the NPs.
A peak at 1624 cm−1 demonstrates the vibration of water
trapped in nano-belts (Fig. 2a).
The nanoparticles represent a superparamagnetic
behavior with saturation magnetization of 65 emu g−1
(Fig. 2b). This behavior could be attributed directly to
the Fe3O4 phases in the nano-belts in accordance with the
FTIR spectrum. The NPs represent an excellent thermal
stability, which there is not found any noticeable weight
loss until 1000 °C. This behavior exhibited that the NPs
are completely inorganic in nature and there are not any
decomposable organic compounds in the NPs. A small
weight loss of ~ 2% at temperature below 200 °C is related
to desorption of water that is trapped in the network of
NPs (Fig. 2c).
Typical procedure for preparation of quinolines
In a typical procedure, to a 25 mL round bottom fask,
2-aminobenzophenone (1.0 mmol) and dimedone
(1.2 mmol) were added to 3 mL of water. The catalyst
(5 mg) was added to the mixture, and the resulting mixture
was stirred at room temperature for an appropriate time.
The reaction progress was monitored by TLC. Upon the
reaction completion, 5 mL of ethanol was added to the
mixture and the catalyst was separated by an external mag-
netic feld. Then, the product was extracted with EtOAc
(7 mL × 3). The organic phases were combined, and the
solvent was removed under reduced pressure. The crude
product was recrystallized with EtOH to aford the pure
quinoline product.
From XRD pattern of nano-belts, various phases
including Fe3O4, CrO2, and NiO could be seen. The peaks
appeared at 2θ = 29.7°, 36.6°, 43.3°, 53.5°, and 62.9°
Fig. 2 FTIR spectrum (a), b VSM curve, c TGA curve, and d XRD spectrum of the Fe–Cr–Ni oxide alloy nanoparticles
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Journal of the Iranian Chemical Society
correspond to the (220), (311), (400), (422), (440) planes
that are related to the inverse spinel crystal structure of
Fe3O4 (Fig. 2d, black circles) [38]. The characteristic
difraction peaks at 2θ = 37.3°, 43.5°, 62.5°, 75.6°, and
78.4° could be marked, respectively, by their indices to the
(111), (200), (220), (311), and (222) planes, demonstrat-
ing NiO structure [39]. Moreover, two peaks at 2θ = 27.6°
and 36.8° could be assigned to CrO2 crystal structure and
correspond to (110) and (101) planes, respectively [40].
Morphology and shape of the NPs were identifed from
SEM and TEM images. As shown in Fig. 3, the nanoparti-
cles are belt-like in shape with a homogenous morphology.
The nano-belts have an average size of 85 nm.
detected by XPS and EDX analyses (Fig. 4c). Although the
determination of particles size distribution of nano-belts is
challenging due to non-spherical shape, but Liu et al. [35]
introduced an efcient reliable method for this measure-
ment, where the particles size distribution of the nano-belts
was measured using a fxed angle DLS. The results were in
agreement with those from TEM, and the nano-belts have
a mean size of 85 nm with a sharp-narrow peak (Fig. 4d).
As shown in Fig. 4d, a nearly symmetrical size distribution
was obtained for the nano-belts. The specifc surface area
and porosity of the nano-belts were studied by N2 adsorp-
tion–desorption isotherm analysis. Based on the BET iso-
therm, specifc surface area and pore volume of the nano-
belts were obtained 186 m2/g and 1.619 cm3/g, respectively
(Table 1).
The EDX analysis demonstrated the presence of C, O,
Fe, Cr, Ni, Si, and Mn elements in the nano-belts in agree-
ment with a ferritic stainless steel 304 chemical composi-
tion (Fig. 4a). Also, the major components were Fe, O, Cr,
and Ni with 37.58, 44.33, 12.87, and 3.60 wt%, respectively
(Fig. 4a-inset table). The presence of the elements was also
confrmed by XPS analysis of the nano-belts completely
in agreement with the EDX analysis. The corresponding
bonding energies are assigned in Fig. 4b. The result from
XRF analysis did not show any other heavy metals that were
2p High-resolution XPS analysis was performed to inves-
tigate the detailed elemental information and the oxidation
state of Fe–Cr–Ni oxide alloy. Figure 5a-d shows the bind-
ing energies related to Cr2p, Mn2p, Fe2p, and Ni2p. Cr 2p
XPS spectrum of the alloy and clearly proved the presence
of CrO2 phases with their corresponding binding energies
at 576.4 eV (Cr 2p3/2) and 586.4 eV (Cr 2p1/2) in agreement
with the literature (Fig. 5a) [41, 42]. High-resolution XPS
Fig. 3 SEM (a, b), and TEM (c, d) images of Fe–Cr–Ni oxide alloy nanoparticles
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Fig. 4 EDX (a), XPS (b), XRF (c), and DLS (d) spectra of the Fe–Cr–Ni alloy nanoparticles
Table 1 Surface characteristics of Fe–Cr–Ni oxide alloy
XRD crys- TEM Specifc Pore
Ni 2p spectrum represents two edge splits by spin orbital
coupling including 2p3/2 and 2p1/2 at ~ 854 and ~ 872 eV,
respectively (Fig. 5d). Also, their corresponding satellites
were appeared at 862.1 and 879.0 eV, respectively, which
confrmed the existence of NiO phases in Fe–Cr–Ni oxide
alloy [46, 47].
Average pore
radius (nm)
talline size particle size surface area volume
(mn)
(nm)
(m2/g)
186
(cm3/g)
1.619
69
85
2.577
Catalytic activity
spectrum of Mn 2p showed two couples characteristic peaks
In order to investigate the parameters involved in the reac-
tion, the reaction of benzaldehyde with dimedone was
chosen as a model reaction for the preparation of 9-phenyl-
3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione. First of
all, the reaction was conducted in various types of solvents
(Table 2). The best choice was water as a green solvent with
90% conversion at room temperature; although some other
solvents such as EtOH, PEG-200, glycerol, and DMSO
afforded same and/or slightly higher conversion, since
environmental and industrial aspects, water was selected
at (640.5, 652.0 eV) and (642.0, 653.0) related to (Mn 2p3/2
,
Mn 2p1/2) for Mn3+ and Mn4+, respectively (Fig. 5b) [43].
Although the Mn content in the alloy is very low (1.02 wt%
based on EDX analysis), the presence of Mn oxides, Mn2O3,
and MnO2 is likely due to the presence of +3 and +4 nuclei
in the alloy (Fig. 5b). For the Fe 2p XPS spectrum, two
spin–orbit splitted represent the existence of both Fe2+ and
Fe3+ in Fe3O4 phases (Fig. 5c) [44]. The peaks at 710.0
(2p3/2) and 723.4 (2p1/2) eV correspond to Fe2+, and 711.8
(2p3/2) and 725.5 (2p1/2) eV are related to Fe3+ [45]. The
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Journal of the Iranian Chemical Society
Fig. 5 High-resolution XPS (energy-corrected) analysis of Fe–Cr–Ni oxide alloy: a Cr 2p, b Mn 2p, c Fe 2p, and d Ni 2p
Table 2 Optimization experiments for the reaction of benzaldehyde,
cause a noticeable change in efciency. The vital role of the
dimedone catalyzed by Fe–Cr–Ni alloy
catalyst was elucidated when the reaction was carried out in
the absence of the catalyst, and a trace amount was obtained
(Table 2).
Entry
Solvent
Cat. amount Time (min)
(mg)
Yield (%)
After fnding the optimum conditions for the preparation
of xanthene compounds, various derivatives of aldehyde
were condensed with dimedone or 1,3-cyclohexadione in the
presence of 5.0 mg of catalyst in water at room temperature.
The results are tabulated in Table 3. As shown in Table 3,
a wide scope of aldehyde-bearing electron-donating group
(3b, 3c, 3g, 3h, 3u, 3v, …) or electron-withdrawing group
(3d, 3e, 3i, 3j, 3o, 3p, …) could be transferred to xanthenes
with high efciency (74–96%, 30–85 min). This diversity
refects the compatibility of the catalyst toward a variety of
functional groups, which acid sensitive aldehydes such as
thiophene-2-carbaldehyde (Table 3, entry 12) and furfural
(Table 3, entry 13) could be efciently transformed to the
corresponding xanthenes.
1
2
3
4
5
6
7
8
H2O
5.0
5.0
5.0
5.0
5.0
5.0
5.0
3.0
4.0
6.0
8.0
–
65
65
65
80
80
120
120
80
80
80
90
90
92
90
88
75
45
65
85
EtOH
DMSO
Glycerol
PEG-200
CH3CN
DEE
H2O
H2O
H2O
H2O
9
10
11
12
90
91
80
180
H2O
Trace
Reaction conditions: dimedone (2.2 mmol), benzaldehyde
(1.0 mmol), catalyst, solvent (3.0 mL), room temperature
Encouraged by the obtained results from the preparation
of xanthenes, we then examined the versatility and general-
ity of this method toward the preparation of quinolines. As
shown in Table 4, again, a wide variety of carbonyl com-
pounds whether aliphatic or aromatic (5) were condensed
with 2-aminobenzophenone and/or 2-amino-5-chlorbenzo-
phenone (4b), and high to excellent yields were achieved
for all of entries.
as the premium solvent in our study. The highest possible
efciency was obtained in the presence of only 5.0 mg of
catalyst in water, which give 90% conversion for 65 min
(Table 2).
All experiments were performed at room temperature;
it should be noted that the increase in temperature did not
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Journal of the Iranian Chemical Society
Table 3 Preparation of 1,8-dioxo-octahydroxanthenes (3a–3ac) cata-
Table 4 Preparation of quinoline derivatives (6a–6r) catalyzed by
lyzed by Fe–Cr–Ni nano-belts in water at room temperature
Fe–Cr–Ni nano-belts in water at room temperature
Entry R1
R2 Product Time (min) Yield (%)
Entry
4
5
Product Time (min) Yield (%)
1
2
3
4
5
6
7
8
Phenyl
H
H
H
H
H
H
H
H
H
H
3a
3b
3c
3d
3e
3f
65
50
55
70
50
45
50
45
35
30
60
70
60
60
60
60
80
45
85
60
80
40
55
80
45
80
75
40
85
90
88
86
82
92
90
86
89
97
97
96
98
98
80
96
98
76
79
89
73
76
82
83
74
94
78
90
96
85
4-Me-phenyl
4-OMe-phenyl
4-Cl-phenyl
3-Cl-phenyl
3-Me-phenyl
2-OH-phenyl
4-OH-phenyl
4-NO2-phenyl
3-NO2-phenyl
Phenyl
2-Thiophene
2-Furyl
2,5-diMeO-phenyl Me 3n
2-Pyridil
1
2
3
4
5
6
7
8
4a 1,3-Cyclohexanone
4a Methyl acetoacetate
4a Cycloheptanone
4a Acetophenone
4b Ethyl acetoacetate
4b 1,3-cyclohexanone
4a 4′-MeO-acetophenone 6g
4a 4′-OH-acetophenone 6h
4b 4′-Cl-acetophenone
4a 4′-NO2-acetophenone 6j
4a Cyclohexanone
4b 4′-Cl-acetophenone
4a Cyclopentanone
4b Acetophenone
4b Acetylacetone
4b Dimedone
6a
6b
6c
6d
6e
6f
50
35
38
35
60
40
32
35
50
50
60
40
45
66
85
30
40
30
90
98
98
95
85
88
98
92
88
86
95
98
93
86
82
97
80
80
3g
3h
3i
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
3j
9
6i
Me 3k
Me 3l
Me 3m
10
11
12
13
14
15
16
17
18
6k
6l
6m
6n
6o
6p
6q
6r
Me 3o
Me 3p
Me 3q
Me 3r
Me 3s
Me 3t
Me 3u
Me 3v
Me 3w
Me 3x
Me 3y
Me 3z
Me 3aa
Me 3ab
Me 3ac
3-Pyridil
2-Naphthyl
4-Me-phenyl
2-NO2-phenyl
3-Me-phenyl
2-OH-phenyl
4-OH-phenyl
4-Br-phenyl
4-Cl-phenyl
4-I-phenyl
2-MeO-phenyl
4-NO2-phenyl
3-NO2-phenyl
4-MeO-phenyl
4a Acetylacetone
4a 4′-Cl-acetophenone
Reaction conditions: 2-aminobenzophenone (1.0 mmol), carbonyl
compound (1.2 mmol), catalyst (5.0 mg), water (3.0 mL), room tem-
perature
Reaction conditions: 1,3-dione (2.2 mmol), aldehyde (1.0 mmol), cat-
alyst (5.0 mg), water (3.0 mL), room temperature
Recyclability studies
The main advantage of a heterogeneous catalyst is its ability
to recover from the reaction medium and use it repeatedly
without compromising efciency [36, 37, 48]. This property
is very important in terms of economic, industrial objectives,
and environmental sustainability. In this way, both reactions
of (1) dimedone with benzaldehyde (preparation of 3a), and
(2) 2-aminobenzophenone with 1,3-cyclohexadione (prepa-
ration 6a) were performed several consecutive times under
Fig. 6 Studies of recycling of the catalyst during the successive reac-
tion cycles for the preparation of 3a and 6a
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Journal of the Iranian Chemical Society
Table 5 Measurement of
leaching amount in each
Element
Leaching amount in each run (μg L−1
)
reaction cycle for the reaction of
benzaldehyde and dimedone for
the preparation of 3a
Run 1
Run 2
Run 3
Run 4
Run 5
Run 6
Run 7
Run 8
Cr
Ni
Fe
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.006
0.005
0.000
0.008
Mn
Reaction conditions: 1,3-dione (2.2 mmol), aldehyde (1.0 mmol), catalyst (5.0 mg), water (3.0 mL), room
temperature
The analyses for Cr, Ni, Fe, and Mn were taken at 205.552 nm, 231.604 nm, 259.940 nm, and 257.610 nm,
respectively
optimized conditions. Figure 6 shows the corresponding
results that insignifcant loss in efciency was observed at
the eighth run. There is only a 3% loss in product yield was
achieved for both reactions (Fig. 6). In addition, metal leach-
ing in the catalyst was studied for the reaction of dimedone
with benzaldehyde (preparation of 3a). Due to the presence
of various transition metals in the catalyst, the leaching was
determined for each of them in every cycle. Table 5 shows
these amount for Cr, Ni, Mn, and Fe, which there are not sig-
nifcant. However, an ignorable amount was detected for the
elements after the eight run except Fe (Table 5). To support
these results, the hot fltration test was applied for this reac-
tion. The catalyst was magnetically fltered from the reaction
mixture of benzaldehyde and dimedone after 30 min at room
temperature. The efciency was 49% (GC) in this time. The
reaction was allowed to proceed for another 1 h, where the
Fig. 7 FTIR (a) and EDX (b) spectra, SEM (c) and TEM (d) images of the Fe–Cr–Ni oxide alloy nanoparticles
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Journal of the Iranian Chemical Society
5. M.K. Barman, A. Jana, B. Maji, Adv. Synth. Catal. 360(17),
3233–3238 (2018)
yield reached to 50%. This indicates that the catalyst acts
heterogeneously and it does not sufer any metal leaching
during the reaction. These results refect the heterogeneous
nature of the catalyst which maintains its catalytic activity
during recycling.
6. A.H. Suja, S. Sugunan, Bull. Catal. Soc. India 2, 194–203 (2003)
7. Z.G. Le, M. Liang, Z.S. Chen, S.H. Zhang, Z.B. Xie, Molecules
22, 762–770 (2017)
8. S.Y. Lee, C.H. Cheon, J. Org. Chem. 83(21), 13036–13044 (2018)
9. R. Sharma, P. Kour, A. Kumar, J. Chem. Sci. 130(6), 73–98 (2018)
10. A.T. Garrison, Y. Abouelhassan, H. Yang, H.H. Yousaf, T.J.
Nguyen, R.W. Huigens, MedChemComm 8(4), 720–724 (2017)
11. F. Tufail, M. Saquib, S. Singh, J. Tiwari, M. Singh, J. Singh, J.
Singh, New J. Chem. 41(4), 1618–1624 (2017)
To show the stability and durability of the catalyst, it was
characterized after the eight recycling test (Figs. 6 and 7). As
shown in Fig. 7 and with the comparison with the fresh ones,
the FTIR and EDX spectra as well as SEM and TEM images
confrmed that the structure of the catalyst is as same as the
fresh one and there is not any change in its structure during
several recycles. FTIR and EDX spectra strongly confrmed
the structure and morphology of the catalyst. Also, from the
recovered SEM and TEM spectra, it could be concluded that
the structure and morphology of the catalyst remain intact
during the recycles (Fig. 7a–d).
12. R. Rubio-Presa, S. Suárez-Pantiga, M.R. Pedrosa, R. Sanz, Adv.
Synth. Catal. 360(11), 2216–2220 (2018)
13. A. Singhal, P. Kumari, S.M.S. Chauhan, Curr. Organocatal. 4(3),
182–188 (2017)
14. E. Soleimani, M. Naderi Namivandi, H. Sepahvand, Appl. Orga-
nomet. Chem. 31(2), e3566–e3574 (2017)
15. M. Godino-Ojer, E. Soriano, V. Calvino-Casilda, F.J. Mal-
donado-Hódar, E. Pérez-Mayoral, Chem. Eng. J. 314, 488–497
(2017)
16. J. Palaniraja, P. Arunachalam, U. Vijayalakshmi, M.A. Ghanem, S.
Mohana Roopan, Inorg. Nano-Met. Chem. 47(6), 946–949 (2017)
17. N. Azizi, F. Abbasi, M. Abdoli-Senejani, ChemistrySelect 3(13),
3797–3802 (2018)
Conclusion
18. R.M. Naidu Kalla, R.S. Karunakaran, M. Balaji, I. Kim, Chemis-
trySelect 4(2), 644–649 (2019)
A new approach for the top-down preparation of nanoparti-
cles has been developed via the chemical decomposition of
bulk metal alloys using the NaOCl/HNO3/DMSO reagent
as an extraordinary oxidizing/corrosion mixture. In this
study, magnetic Fe–Cr–Ni oxide nano-belts were prepared
by chemical decomposition of a ferritic stainless steel-304
in two steps. The nano-belts demonstrated an excellent
catalytic activity toward the preparation of quinolines and
1,8-dioxo-octahydroxanthenes in water at room tempera-
ture, which high to excellent yields were obtained for all
compounds. The nano-belts have a diameter of about 80 nm
and have sufcient magnetization of 65 emu g−1, and also
high thermal and mechanical resistance. The catalyst could
be recycled for at least eight consecutive runs without any
signifcant loss in its activity.
19. M. Seyyedhamzeh, P. Mirzaei, A. Bazgir, Dyes Pigments 76(3),
836–839 (2008)
20. E. Böβ, T. Hillringhaus, J. Nitsch, M. Klussmann, Org. Biomol.
Chem. 9(6), 1744–1748 (2011)
21. A. Jha, J. Beal, Tetrahedron Lett. 45(49), 8999–9001 (2004)
22. C.W. Kuo, J.M. Fang, Synth. Commun. 31(6), 877–892 (2001)
23. R.J. Sarma, J.B. Baruah, Dyes Pigments 64(1), 91–92 (2005)
24. P. Bansal, N. Kaur, C. Prakash, G.R. Chaudhary, Vacuum 157,
9–16 (2018)
25. A. Ilangovan, S. Malayappasamy, S. Muralidharan, S. Marutha-
muthu, Chem. Cent. J. 5(1), 81–87 (2011)
26. T. Ikeno, T. Nagano, K. Hanaoka, Chem. Asian J. 12(13), 1435–
1446 (2017)
27. M.A. Poursattar, S. Abdollahi, M. Ezzati, E. Nemati-Kande, J.
Heterocycl. Chem. 55(6), 1324–1330 (2018)
28. J. Safari, P. Aftabi, M. Ahmadzadeh, M. Sadeghi, Z. Zarnegar, J.
Mol. Struct. 1142, 33–39 (2017)
29. N. Mulakayala, G.P. Kumar, D. Rambabu, M. Aeluri, M.B. Rao,
M. Pal, Tetrahedron Lett. 53(51), 6923–6926 (2012)
30. P. Bansal, G.R. Chaudhary, N. Kaur, S.K. Mehta, RSC Adv. 5(11),
8205–8209 (2015)
Acknowledgements The authors are grateful to the University of
Birjand for fnancial support.
31. M.S. Patil, A.V. Palav, C.K. Khatri, G.U. Chaturbhuj, Tetrahedron
Lett. 58(29), 2859–2864 (2017)
Compliance with ethical standards
32. A. Khazaei, A.R. Moosavi-Zare, Z. Mohammadi, A. Zare, V.
Khakyzadeh, G. Darvishi, RSC Adv. 3(5), 1323–1326 (2013)
33. H. Naeimi, Z.S. Nazif, J. Nanopart. Res. 15(11), 2026 (2013)
34. F. Shirini, M.S.N. Langarudi, M. Seddighi, O.G. Jolodar, Res.
Chem. Intermed. 41(11), 8483–8497 (2015)
Conflict of interest There are no confict to declare.
35. C. Dhand, N. Dwivedi, X.J. Loh, A.N.J. Ying, N.K. Verma, R.W.
Beuerman, R. Lakshminarayanan, S. Ramakrishna, RSC Adv.
5(127), 105003–105037 (2015)
References
36. S. Ghiami, M.A. Nasseri, A. Allahresani, M. Kazemnejadi, React.
Kinet. Mech. Catal. 126(1), 383–398 (2019)
1. D.G. Shchukin, G.B. Sukhorukov, Adv. Mater. 16(8), 671–682
(2004)
37. M. Kazemnejadi, Z. Rezazadeh, M.A. Nasseri, A. Allahresani, M.
Esmaeilpour, Green Chem. 21(7), 1718–1734 (2019)
38. A.R. Sardarian, M. Kazemnejadi, M. Esmaeilpour, Dalton Trans.
48(9), 3132–3145 (2019)
2. R.P. Feynman, Eng. Sci. 23(8), 22–36 (1960)
3. F.E. Kruis, H. Fissan, A. Peled, J. Aerosol Sci. 29(5–6), 511–535
(1998)
4. J. Jeevanandam, A. Barhoum, Y.S. Chan, A. Dufresne, M.K. Dan-
quah, Beilstein J. Nanotechnol. 9(1), 1050–1074 (2018)
39. M. Ghosh, K. Biswas, A. Sundaresan, C.N.R. Rao, J. Mater.
Chem. 16(1), 106–111 (2006)
1 3

Journal of the Iranian Chemical Society
40. J. Dai, J. Tang, H. Xu, L. Spinu, W. Wang, K. Wang, A. Kumbhar,
M. Li, U. Diebold, Appl. Phys. Lett. 77(18), 2840–2842 (2000)
41. R. Cheng, B. Xu, C.N. Borca, A. Sokolov, C.S. Yang, L. Yuan,
S.H. Liou, B. Doudin, P.A. Dowben, Appl. Phys. Lett. 79(19),
3122–3124 (2001)
45. R. Madhuvilakku, S. Alagar, R. Mariappan, S. Piraman, Sens.
Actuators B 253, 879–892 (2017)
46. W. Huang, S. Ding, Y. Chen, W. Hao, X. Lai, J. Peng, J. Tu, Y.
Cao, X. Li, Sci. Rep. 7(1), 5220–5231 (2017)
47. P.T. Babar, A.C. Lokhande, M.G. Gang, B.S. Pawar, S.M. Pawar,
J.H. Kim, J. Ind. Eng. Chem. 60, 493–497 (2018)
48. M. Kazemnejadi, A.R. Sardarian, RSC Adv. 6(94), 91999–92006
(2016)
42. N.F. Heinig, H. Jalili, K.T. Leung, Appl. Phys. Lett. 91(25),
253102–253104 (2007)
43. M. Kazemnejadi, S.A. Alavi, Z. Rezazadeh, M.A. Nasseri, A.
Allahresani, M. Esmaeilpour, J. Mol. Struct. 1186, 230–249
(2019)
44. F. Han, L. Ma, Q. Sun, C. Lei, A. Lu, Nano Res. 7(11), 1706–1717
(2014)
Afliations
Milad Kazemnejadi1 · Zeinab Sharaf2 · Boshra Mahmoudi3 · Atefeh Zeinali1 · Mohammad Ali Nasseri1
1
3
Department of Chemistry, Faculty of Sciences, University
of Birjand, Birjand 97175-615, Iran
Research Center, Sulaimani Polytechnic University,
Sulaimani 46001, Kurdistan Region, Iraq
2
Razi Herbal Medicines Research Center, Lorestan University
of Medical Sciences, Khorramabad, Iran
1 3