First electrospun immobilized molybdenum complex on bio iron oxide nanofiber for green oxidation of alcohols

Article abstract of DOI:10.1016/j.polymer.2018.07.003

Bio iron oxide was synthesized from natural Sesbania sesban plant and modified by a molybdenum complex (Fe₂O₃/MoSB). Fe₂O₃/MoSB was deposited on polyvinyl alcohol (PVA) using a conventional single nozzle electrospinning technique (PVA/Fe₂O₃/MoSB). TEM, SEM, AFM, FT-IR, TGA, EDAX, and elemental analysis were used to determine fiber compositional information. The catalytic efficiency of electrospun PVA/Fe₂O₃/MoSB nanofiber in the oxidation of alcohols was exploited. The green reactions were conducted at solvent free conditions as a green media in the presence of H₂O₂ to have the desired aldehydes and tert-butyl hydrogen peroxide to obtain acid products in high yields and excellent selectivity. The survival of this nanocomposite was investigated and it could be reused and recycled in consecutive runs.

Full text of DOI:10.1016/j.polymer.2018.07.003

Polymer 149 (2018) 229e237
Contents lists available at ScienceDirect
Polymer
journal homepage: www.elsevier.com/locate/polymer
First electrospun immobilized molybdenum complex on bio iron oxide
nanofiber for green oxidation of alcohols
Sedighe Abbaspour Noghi , Atena Naeimi , Hooshang Hamidian a
a
b, *
a
Department of Chemistry, Payame Noor University of Tehran, Tehran, Iran
Department of Chemistry, Faculty of Science, University of Jiroft, Jiroft, Iran
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 April 2018
Received in revised form
Bio iron oxide was synthesized from natural Sesbania sesban plant and modified by a molybdenum
complex (Fe
single nozzle electrospinning technique (PVA/Fe
elemental analysis were used to determine fiber compositional information. The catalytic efficiency of
electrospun PVA/Fe /MoSB nanofiber in the oxidation of alcohols was exploited. The green reactions
were conducted at solvent free conditions as a green media in the presence of H to have the desired
2
O
3
/MoSB). Fe
2
O
3
/MoSB was deposited on polyvinyl alcohol (PVA) using a conventional
2 3
O
/MoSB). TEM, SEM, AFM, FT-IR, TGA, EDAX, and
22 June 2018
Accepted 1 July 2018
Available online 2 July 2018
2 3
O
2 2
O
aldehydes and tert-butyl hydrogen peroxide to obtain acid products in high yields and excellent selec-
tivity. The survival of this nanocomposite was investigated and it could be reused and recycled in
consecutive runs.
Keywords:
Nanocatalyst
Nanofiber
Composites polymers
© 2018 Elsevier Ltd. All rights reserved.
1. Introduction
thermal and chemical stability, has already been proven as an
effective way to produce new materials with specific properties
Todays, development of electrospun nanocomposites rein-
forced polymer fiber materials with intention to stimulate in-
terests in both academia and industry makes them highly
attractive [1]. Electrospun nanofiber have great potential for
synthesis of next-generation polymer nanofibers [2,3]. Continuity,
diverse material choice, controlled diameter/structure, possible
alignment/assembly, and mass production capability are
comprehensive advantages of electrospun nanopolymers [3e5].
Inorganic nanofibers, with smaller pores and higher surface area
than regular fibers, have enormous catalytic applications [6,7].
Despite enormous efforts devoted to explore industrial applica-
tions of electrospun nanofibers, there are limited attempts to
employ these nanofibers for reinforcement in polymer nano-
hybrids [8,9]. Among all polymers, polyvinyl alcohol (PVA) due
to its low cost, high hydrophilicity, and excellent chemical resis-
tance has used in broad application areas. PVA is a synthetic
water-soluble hydrophilic polymer and the degree of polymeri-
zation or the degree of hydrolysis can effect on its properties such
as adhesives, emulsificantes, and paper industry applications
and high performances [11e13]. In many recent studies, iron
nanoparticles (NPs) for environmental remediation have indi-
cated excellent potentials [14,15]. Microwave assisted synthesis,
ultrasonication assisted synthesis, coprecipitation, chemical
reduction methods, and hydrothermal methods are the methods
for iron oxide synthesis. While, the most commonly used con-
ventional strategy for the synthesis of the nanoparticles are
chemical physical and biological methods [16e18]. However, they
need expensive instruments, high energy, usage of toxic reducing
agents maintaining the cell culture, and recovery steps [19]. The
undesirable features of traditional reagents and methods have
forced chemists to use phyto-mediated synthesis to reduce the
costs of chemical production [20,21]. Hence, the synthesis of
nanoparticles using the plant extract has several advantages
[22e24].
On continuing our work on the green catalytic system
[25e29], bio
plant and molybdenum complex was supported on it and
nanofiber of immobilized molybdenum complex on -Fe in
the presence of PVA was synthesized through electrospinning
2 3
a-Fe O was synthesized using Sesbania sesban
a
2 3
O
[
1,10]. Modified PVA with metal oxides, with different mechanical,
*
Corresponding author.
E-mail address: a.naeimi@ujiroft.ac.ir (A. Naeimi).
https://doi.org/10.1016/j.polymer.2018.07.003
032-3861/© 2018 Elsevier Ltd. All rights reserved.
0

230
S.A. Noghi et al. / Polymer 149 (2018) 229e237
2 3
Scheme 1. The synthesis of electrospun PVA/Fe O /MoSB nanofiber.
(
PVA/Fe
2
O
3
/MoSB). As our acknowledgment, this work is the
procured from Alderich and Merk Company, respectively. FT-IR
spectra were recorded by FT-IR spectrophotometer (NICOLET
first report of catalytic potential of an electrospun nanofiber
base on one transition metal complex in oxidation reactions.
2 3
iS10). Thermo stability of PVA/Fe O /MoSB was investigated by
Here, we describe catalytic properties of PVA/Fe
the presence H as an ideal oxidant to aldehyde products
common oxidant to produce the acid
2
O
3
/MoSB in
Simultaneous Thermal Analyzer. Synthesis of iron oxide nano-
particles was performed by furnace (FANAZMA GOSTAR). Shape
2 2
O
and t-BuOOH as
products.
a
and morphology of PVA/Fe
microscope (Philips CM30). X-ray energy-dispersive spectroscopy
EDS) detector (IE 300X,Oxford, UK) attached to the SEM was
analyzed the elemental composition of materials. For AFM im-
ages of PVA/Fe /MoSB, an atomic force microscopy (DME
Model Igloo) was performed. Electrospinning instrument was
2 3
O /MoSB was considered by TEM
(
2
. Material and methods
2 3
O
Sesbania sesban was provided from University of Jiroft. 2-
amino pyridine was purchased from Across Company. 3-
chloropropyltrimethoxysilane and Polyvinyl alcohol were
used for synthesis of PVA/Fe
Iran).
2 3
O /MoSB (Nanoazma company,

S.A. Noghi et al. / Polymer 149 (2018) 229e237
231
3.2. Synthesis of immobilized molybdeum complex on
2 3 2 3
functionalized a-Fe O (Fe O /MoSB)
A mixture of 3-chloropropyltrimethoxysilane (0.5 mmol, 0.1 mL)
and triethylamine as a catalyst (0.01 mL, 0.07 mmol) was added to
suspend iron oxide (0.1 g) in dry ethanol (20 mL) and was refluxed
for 24 h. Chloro functionalized iron oxide was separated by
centrifuge machine at 3000 rpm for 5 min and washed with
toluene and water mixture for three times. The resulting product
was dried under vacuum.
0.94 gr of chloro-functionalized iron oxide was added to 2.5 mg
of 2-amino pyridine in ethanol (20 ml) and this reaction mixture
ꢀ
was heated to 80 C for 8 h. The resulting ligand (Fe
2
O
3
/SB) was
separated through centrifugation at 300 rpm for 5 min and washed
three times by ethanol and dried at room temperature [31,32]. 2.31
gr of ammonium hepta molybdate salt was added to suspension of
supported ligand of iron oxide (0.2 gr) in 4 ml of distilled water and
ꢀ
refluxed for 8 h at 80 C. The F
2
O
3
/MoSB washed three times with
distilled water and dried at room temperature.
.3. Electrospinning procedure of Fe /MoSB (PVA/Fe
gr of Fe /MoSB was dispersed to 4 mL of water within a half
3
2
O
3
2 3
O /MoSB)
4
2 3
O
hour and was added to 1.6 gr of PVA in 12 mL of water. The mixture
of reaction was irradiated with ultrasound for 30 min. Prepared
ꢀ
solution was placed under magnetic stirrer for 8 h at 80 C.
The electrospinning of final prepared solution was done at an
electrical voltage of 25 kV at room temperature under atmospheric
pressure. The polymer fibers were injected using a syringe needle
(5 ml) with a needle [1.23 mm outer diameter (OD) and 0.83 mm
internal diameter (ID)] at a flow rate of 0.3 ml/h. The grounded
target was placed at 12 cm from the needle tip.
2 2
3.4. General procedure for oxidation of alcohols using H O
To a mixture of alcohol (1 mmol) and electrospun PVA/Fe
2 3
O /
MoSB nanocomposite (0.003 g) under solvent free conditions,
0
.6 mmol H
2
O
2
(12
m
L) was added and the reaction mixture was
ꢀ
stirred at 80 C for 7 h.
3.5. General procedure for oxidation of alcohols using t-BuOOH
2 3
To a mixture of alcohol (1 mmol) and electrospun PVA/Fe O /
MoSB nanocomposite (0.005 g), 0.6 mmol t-BuOOH (57 mL) was
added under solvent free conditions and the reaction mixture was
ꢀ
stirred at 80 C for 6 h.
3.6. Reusability of catalyst
2 3 2 3
Fig. 1. The FT-IR of PVA, Fe O /MoSB, and PVA/Fe O /MoSB.
2 3
To a mixture of benzyl alcohol (1 mmol, 0.1 mL) and PVA/Fe O /
MoSB nanofiber (0.003 g) under solvent free conditions was added
H O (0.6 mmol, 12 L) and the reaction mixture was stirred at
0 C for 7 h. After completion of the reaction, 1 mL ethyl acetate
was add and catalyst was separated by centrifugation. PVA/Fe O /
3
. Experimental
m
2
2
ꢀ
8
3.1. Green synthesis of iron oxide (a-Fe O )
2 3
2
3
MoSB nanocomposite as the isolated solid phase was dried under
air and reused for next runs. According to the above-mentioned
procedure, catalyst recovery was also considered in the oxidation
of benzyl alcohol under solvent free conditions using t-BuOOH as
an oxidant.
4
gr of Sesbania sesban wood powder was added to 200 ml of
ꢀ
distilled water at 90 C for 10 min. A KOH solution (0.01 M) was
then added drop wise (drop rate ¼ 1 mL.min-1) at room tempera-
ture to reach the reaction pH to 9. 170 ml of the obtained extraction
solution was added to 130 ml of distilled water and 200 ml of
FeCl
3
.6H
2
O solution (0.05 M). The mixture of reaction was heated to
-Fe was separated by an external
4. Result and discussion
ꢀ
8
0 C for 2.5 h. The resulting
a
2 3
O
magnet, washed with water and dried in oven under vacuum. The
as-synthesized sample was heated by the furnace at 250 C for 7 h
Bio iron oxide nanoparticles was synthesized by Sesbania ses-
ꢀ
ban and these green
react with an
2 3
a-Fe O nanoparticles were then allowed to
[
30].
appropriate
concentration
of
3-

232
S.A. Noghi et al. / Polymer 149 (2018) 229e237
2 3
Fig. 2. The analysis spectrum of the PVA/Fe O /MoSB.
Table 1
vibrations of an alcoholic O-H. The bands observed at 1440 and 640
cmꢁ1 are corresponded to the CH bending and stretching modes
[8,10,33]. In the case of Fe /MoSB, the C-O stretching vibration
[2,5,8]. The band observed at around
2 3
The weight percentage of each element in the PVA/Fe O /MoSB.
2
Element
Series
Wt%
At%
2 3
O
ꢁ1
appeared at 1130 cm
Carbon
Nitrogen
Oxygen
Aluminum
Chlorine
Iron
K series
K series
K series
K series
K series
K series
L series
46.06
3.51
41.72
7.80
0.01
0.08
0.69
54.83
3.59
37.28
4.14
0.0
ꢁ
1
627e648 cm was assigned to the stretching vibrations of Metal-
Oxygen (Fe-O) bond in this bio iron oxide nanoparticles [34]. The
ꢁ1
peaks observed at 2910, 2930 and 1475 cm in the FT-IR spectrum
2 3 2
of Fe O /MoSB was related to the stretching and bending of the CH
0.02
0.1
bonds, respectively [35]. Si-O stretching bond was detected in the
Molybdenum
ꢁ
1
ꢁ1
region 1000e1110 cm . A stretching vibrational about 3434 cm
ꢁ1
are attached to the O-H surface. Observed peak at 1629 cm is
confirmed a stretch for the vibrational mode of water. It is the V2
bending mode of the water molecules adsorbing on the surface. In
the FT-IR spectrum of PVA/Fe
2
O
3
/MoSB, additional stretches at
ꢁ1
2957 and 2834 cm are related to aryl CeH stretches. The amine
ꢁ
1
group stretch is found at 1292 cm (C-N). The peaks at 1610, 1496,
ꢁ1
ꢁ1
and 763 cm for the 2-amino pyridine, and 462 cm for MoeN
bond were indicated a minor amount of complex in the structure
of PVA/Fe O /MoSB [36]. Therefore, FT-IR of PVA/Fe O /MoSB
2 3 2 3
confirmed the presence of the supported molybdenum complex on
bio-iron oxide nanoparticles in this nanocomposite.
Also, EDAX measurements (see Fig. 2) provided the direct evi-
dence for chemical analysis. The presence of Fe Mo, Si, Cl, C, and O
2 3
were confirmed as elements in PVA/Fe O /MoSB. The strong signal
was due to the alumina from the Al substrate on which the fibers
were collected [2]. The weight percentage of each element shows in
Table 1. The high percentage of oxygen suggests the presence of
PVA polymer with high number of OH groups in the sample.
2 3
Fig. 3. TGA curves of PVA/Fe O /MoSB composite nanofibrous (dash line) and PVA.
The thermal behavior of PVA and PVA/Fe
nanofiber was analyzed through thermal gravimetric analysis
Fig. 3, dash line) [37]. The thermal stability and content of organic
2 3
O /MoSB composite
(
chloropropyltrimethoxysilane to give chloro-functionalized
Fe . The obtained chloro-functionalized iron oxide was reacted
with 2-amino pyridine to produce immobilized 2-amino pyridine
on bio chloro-functionalized iron oxide (Fe /SB). To this end, the
reaction of Fe /SB with ammonium heptamolybdate in water led
to the formation of F /MoSB. Nanofiber of PVA/Fe /MoSB was
/MoSB base on polyvinyl
a-
functional groups on the surface were considered. The PVA nano-
2
O
3
ꢀ
fiber had three main weight loss stages: the first one, up to 210 C
was related to the evaporation of water and volatile compounds.
2
O
3
ꢀ
From 230 to 380 C, we have second stage corresponding to the
2
O
3
ꢀ
polymer chain. At higher than 400 C, the breakage the main chain
2
O
3
2 3
O
of PVA was happened [38]. By comparison, the PVA nanofiber un-
synthesized by electrospinning of F
alcohol as a polymer (Scheme 1).
2
O
3
ꢀ
dergoes total thermal oxidation between 460 and 700 C, the
presence of Fe
after the polymer decomposition in PVA/Fe
molybdenum complex [39]. According to the TGA curves, the
2
O
3
/MoSB was confirmed. In fact, the remaining mass
2 3 2 3
FT-IR spectra of PVA, Fe O /MoSB, and PVA/Fe O /MoSB were
2 3
O /MoSB is due to the
shown in Fig. 1. In the case of PVA, the most intensive band that
ꢁ
1
appeared at 3900 cm corresponds to the asymmetric stretching

S.A. Noghi et al. / Polymer 149 (2018) 229e237
233
Scheme 2. Oxidation of alcohols catalyzed by PVA/Fe
2
O
3
/MoSB under solvent free
condition using H
acid products.
2 2
O and t-BuOOH to obtain corresponding aldehyde or ketones and
amount of transition metal complex in PVA/Fe
2
O
3
/MoSB is esti-
mated to be 5%.
In continuing our characterization of PVA/Fe O /MoSB com-
2 3
posite nanofibrous, the TEM images of the pure nanofibers with
different diameters showed the uniform structures (Fig. 4a). When
this nanocomposite nucleate and grow during the electrospinning
process, the Fe O /MoSB move to the surfaces of the nanofibers
2 3
PVA because of the internal radial orientation of the electrostatic
field and the rapid evaporation of the solvents. In fact, Fig. 4a shows
2 3
the high-resolution TEM image of the PVA/Fe O /MoSB nanofiber
and the short distances of straight chain separated each other [40].
The PVA chains are elongated and self-oriented side by side along
the fiber axis and the straight molecular segments in these chains
are at least 40e70 nm long. Also, the SEM of PVA/Fe
confirmed the irregular white and gray dots on the straight chain of
2 3
PVA, which are Fe /MoSB (Fig. 4b). The aggregation of the Fe O /
2 3
O /MoSB
2
O
3
MoSB was observed and the average size of them was estimated
about 30 nm.
Two-dimensional (Fig. 4c) and three-dimensional (Fig. 4d) AFM
2 3
topography images of PVA/Fe O /MoSB were used to determine
fiber compositional information. Representative AFM-phase was
gave good information about surface morphology this nanofiber.
AFM images were derived from 5.1
m m * 5.1m m scans part of the
samples. The AFM-phase image (Fig. 4a) shows the aggregation of
the hydrophobic parts of the immobilized molybdenum complex
on iron oxide nanoparticles in the PVA/Fe
dimensional AFM topography image, 5.1
showed that nanofibers with high porosity was formed [43].
2 3
O /MoSB [41,42]. Three-
2
m
m *1.1 mm framework,
4.1. Green oxidation of alcohols catalyzed by PVA/Fe
2 3
O /MoSB
Catalytic potential of PVA/Fe /MoSB was evaluated in the
2 3
O
oxidation of alcohols as green chemistry point of view (Scheme 2).
Different factors such as various temperatures, solvents, catalyst
amounts, and oxidants were optimized in the oxidation of alcohols
catalyzed by PVA/Fe
composite was initially evaluated for the oxidation of benzyl
alcohol with H as ideal oxidant under solvent free conditions as
a green media. This reaction did not proceed in the absence of the
catalyst under any conditions [44]. While, PVA/Fe /MoSB
0.003 g) was used into the reaction mixture, the conversion rate
was enhanced significantly and benzaldehyde was obtained in 65%
2 3
O /MoSB nanofiber (Fig. 5). This nano-
2 2
O
Fig. 4. TEM image (a), SEM image (b), two-dimensional (4c) and three-dimensional
4 d) AFM topography images of electrospun PVA/Fe /MoSB nanofiber.
2 3
O
(
2 3
O
(

234
S.A. Noghi et al. / Polymer 149 (2018) 229e237
2 3
Fig. 5. The effect of solvents (a), catalyst amount (b), temperature (c), time (d), and oxidant (e) on the oxidation of alcohols catalyzed by electrospun PVA/Fe O /MoSB nanofiber.
ꢀ
and 100% yield after 5 and 7 h at 80 C, respectively. When the same
was produced the benzoic acid as sole product. It seem that t-
amount of PVA, Fe
2
O
3, and Fe
2
O
3
/MoSB was applied as heteroge-
BuOOH is a strong oxidant, even more effective than hydrogen
peroxide, therefore, it was used in the agrochemical and pharma-
ceutical industries instead of other organic peroxides [40]. Oxida-
neous catalysts in this green system. Trace, 20, 44% of related
products were achieved, respectively. Virtually, no catalytic activity
was observed in commonly used organic solvents. The examination
of six solvents, such as dichloromethane (DCM), dichloroethane
tion of benzyl alcohol under the optimized conditions (0.005 g of
ꢀ
PVA/Fe
2
O
3
/MoSB under solvent free conditions at 80 C within 6 h)
(
DCE), acetonitrile (MeCN), methanol (MeOH), ethanol (EtOH),
water (H O) and solvent free conditions, showed that solventless
and acetonitrile promoted the yield of the aldehyde products
Fig. 5a). Solvent free conditions were selected due to easy sepa-
using 0.06 mmol of t-BuOOH, gave solely benzoic acid in 100% yield
(Support information, S1-S4).
2
PVA/Fe
ward oxidation of a wide range of primary and secondary alcohols
under optimized conditions using H and t-BuOOH (Table 2). The
2 3
O /MoSB was shown high efficiency and selectivity to-
(
ration of the products and catalyst. On the other hand, the yields of
reactions were crucially affected by the catalyst amounts. Best yield
of aldehyde product was achieved by using 0.003 g of the electro-
spun nanofiber (Fig. 5b). It seems that higher temperatures up to
8
2 2
O
secondary alcohols were subjected in this green system and high
conversion and excellent selectivity were achieved. Generally, the
secondary alcohols were oxidized more difficult than of primary
alcohols. Ester products were not observed in this clean strategy
(Table 2, entries 1e4). A number of primary substituted benzylic
alcohols, like benzyl alcohol, were oxidized smoothly to their cor-
ꢀ
0 C was required to furnish favored yields of the benzaldehyde
2 3
under the catalytic influence of PVA/Fe O /MoSB (Fig. 5c). Under
these optimum conditions, benzyl alcohol converted completely to
the related aldehyde product within 7 h (Fig. 5d). To consider the
oxidizing potential of other common oxidants, benzyl alcohol was
2 2
responding aldehydes using H O and acid products in the pres-
ence of t-BuOOH (Table 2, entries 5e12). It should be noted the
electronic and steric demands of the substrate could effect on the
yield of products. In fact, by changing the oxidant, the formation of
acid or aldehyde products was controlled completely. Desired
aldehyde and acid products were obtained in yields ranging from
85% to quantitative in the presence of both oxidants.
subjected to the oxidation protocol using O
2
, H
2
O
2
, t-butylhy-
, and Oxone , TB (Fig. 5e). The
interesting results were observed at the presence of PVA/Fe
MoSB nanocomposite. At the same condition, benzyl alcohol was
oxidized to benzaldehyde completely using H , while, t-BuOOH
®
droperoxide (t-BuOOH), NaIO
4
2 3
O /
2 2
O

S.A. Noghi et al. / Polymer 149 (2018) 229e237
235
Table 2
The oxidation of different alcohols catalyzed by electrospun PVA/Fe
2
O
3 2 2
/MoSB nanocomposite under solvent free condition using H O and t-BuOOH.
Entry
1
Alcohol
Product
Conversion%(selectivity of aldehyde)a
100
Conversion% (selectivity of acid)b
90
2
90
95
3
4
85
70
100
90
5
6
90 (100)
100 (100)
100 (100)
100 (100)
7
100 (100)
90 (100)
8
9
100 (98)
90 (100)
100 (100)
100 (100)
10
85 (100)
85 (85)
1
1
1
2
95 (100)
90 (100)
100 (90)
90 (95)
a
ꢀ
ꢀ
The reactions were run under air for 7 h at 80 C under solvent free condition using H
2
O
2
as a green oxidant.
b
The reactions were run under air for 6 h at 80 C under solvent free condition using t-BuOOH.
Encouraged by the impressive results obtained for indicating its
relative stability of PVA/Fe /MoSB biopolymer in the heteroge-
same reaction conditions. The average yield of benzaldehyde for
five consecutive runs was 95%, which clearly demonstrates the
practical reusability of this catalyst. These benefits along with
excellent conversion and selectivity of wide range of alcohols using
the present green system were addressed one novel environmental
and industrial strategy.
2 3
O
neous oxidation system, the recycling of the catalyst was investi-
gated (Fig. 6). After performing the oxidation reaction of benzyl
alcohol with this biopolymer nanofiber under the present condi-
tions, EtOAc was added to work-up. The catalyst was separated by
the centrifuge from the reaction mixture, washed with EtOAc, dried
at room temperature, and reused for a consecutive run under the
Ultimately, we compared the result and conditions used in this
work for oxidation of benzyl alcohol (Table 3) with some reports

236
S.A. Noghi et al. / Polymer 149 (2018) 229e237
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[
Acknowledgments
We are thankful to University of Jiroft and Kerman Payame Noor
University for their support on this work.
[
Appendix A. Supplementary data
[
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.polymer.2018.07.003.

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