Magnetic Fe3O4/graphene oxide/copper-based nanocomposite as a reusable catalyst for the reduction of 4-nitrophenol

Article abstract of DOI:10.1166/jnn.2020.16889

In the present investigation, Fe3O4/Graphene oxide/Pr–NH2–CuII was reported as a novel magnetically recoverable nanocomposite and characterized using various analytical techniques such as FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), vibrating sample magnetometry (VSM), X-ray diffraction (XRD), and inductively coupled plasma (ICP). The catalytic performance of the synthesized catalyst was evaluated in the reduction of 4-nitrophenol to 4-aminophenol by an excess amount of sodium borohydride as the source of hydrogen in aqueous solution. The reaction was monitored by UV-vis spectroscopy at ambient temperature. Magnetic nature of the catalyst led to its simple recovery by a permanent magnet and excellent recyclability without appreciable loss of the catalytic activity.

Full text of DOI:10.1166/jnn.2020.16889

Article
Journal of
Nanoscience and Nanotechnology
Vol. 20, 121–127, 2020
Copyright © 2020 American Scientific Publishers
All rights reserved
Printed in the United States of America
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Magnetic Fe O /Graphene Oxide/Copper-Based
3
4
Nanocomposite as a Reusable Catalyst for the
Reduction of 4-Nitrophenol
1
1ꢀ∗
1ꢀ∗
2
2
Mehdi Zabihzadeh , Farhad Shirini , Hassan Tajik , Zahra Shokri , and Shiva Karami
1Department of Chemistry, College of Science, University of Guilan, Rasht, 41335-19141, Iran
Department of Organic Chemistry, Chemistry Faculty, Urmia University, Urmia 5756151818, Iran
2
II
In the present investigation, Fe O /Graphene oxide/Pr–NH –Cu was reported as a novel magnet-
3
4
2
ically recoverable nanocomposite and characterized using various analytical techniques such as
FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray
spectroscopy (EDX), vibrating sample magnetometry (VSM), X-ray diffraction (XRD), and induc-
tively coupled plasma (ICP). The catalytic performance of the synthesized catalyst was evaluated
in the reduction of 4-nitrophenol to 4-aminophenol by an excess amount of sodium borohydride as
the source of hydrogen in aqueous solution. The reaction was monitored by UV-vis spectroscopy
at ambient temperature. Magnetic nature of the catalyst led to its simple recovery by a permanent
magnet and excellent recyclability without appreciable loss of the catalytic activity.
IP: 91.200.81.81 On: Mon, 30 Dec 2019 09:57:25
Keywords: 4-Nitrophen Co lo pR ye r di gu hc tt i: o An ,m eF er ic Oa n- MS Nc iPe sn ,tif Gi cr aP p uh be lni se h eOr sx ide, NaBH , Copper (II)
3
4
4
Supported Catalysts. Delivered by Ingenta
1
. INTRODUCTION
discharge. Many methodologies have been reported for the
removal of 4-nitrophenol from contaminated water such
as photocatalytic degradation [8], catalytic reduction [9],
microwave-assisted catalytic oxidation [10], electrochem-
ical treatment [11], biodegradation [12], electro-Fenton
method [13], and so on. Among the above-mentioned
procedures, the catalytic reduction of 4-nitrophenol to
4-aminophenol in aqueous solution has been proved to be
an efficacious, cost-effective and clean method for this pur-
pose [14]. 4-aminophenol is a vital intermediate for the
synthesis of many analgesic and antipyretic drugs. Also, it
is used extensively as a corrosion inhibitor, photographic
developer, hair-dyeing agent, anticorrosion-lubricant [15].
Hence, it is very important to design an efficient and envi-
ronmentally benign catalytic system for the reduction of
Nitrobenzene and its derivatives are widely used as impor-
tant organic feedstocks in the chemical industry for the
production of dyes, pigments, pharmaceuticals, plastics,
fungicides, pesticides, industrial solvents, and explo-
sives [1, 2]. However, these compounds are highly haz-
ardous to the environment and human health [3]. As a
member of nitroaromatic compounds, 4-nitrophenol is one
of the most refractory organic pollutants which extensively
exists in industrial effluents of chemical plants and agri-
cultural waste-waters [4]. This compound is toxic and
due to its minuscule biodegradability, high stability and
solubility in water is stable in the environment and bio-
logical systems which can cause serious damage to the
central nervous system, liver, and kidney of humans and
animals even at low concentration [5–7]. For this rea-
son, the United States Environmental Protection Agency
4
-nitrophenol to 4-aminophenol.
In recent years, magnetic nanoparticles (MNPs) have
(
EPA) has classified 4-nitrophenol as ‘priority pollutant.’
attracted more attention because of their widespread range
of applications in environmental remediation, drug deliv-
ery, magnetic resonance imaging (MRI), energy storage,
magnetic inks, magnetic fluids, and catalysis [16, 17].
In the field of organic chemistry, the use of MNPs
as catalysts or catalyst supports (magnetic nanoparticles
Therefore, it is of great importance to assess the fate of
this compound in the environment and develop conve-
nient procedures to remove it from waste–water before
∗
Authors to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2020, Vol. 20, No. 1
1533-4880/2020/20/121/007
doi:10.1166/jnn.2020.16889
121

Magnetic Fe O /Graphene Oxide/Copper-Based Nanocomposite as a Reusable Catalyst
Zabihzadeh et al.
3
4
supported catalytic systems) in organic transformations has
become a hot topic of numerous investigations. This is
because MNPs can be easily (via external magnet) sep-
arated and recovered which is very worthwhile from the
viewpoint of economic and environmental issues (green
chemistry) [18, 19].
analysis of Cu was carried out using inductively coupled
plasma-optical emission spectrometry (ICP-OES) (Optima
7300D-PerkinElmer). Magnetization curves were recorded
by a vibrating sample magnetometer (VSM, Meghnatis
Daghigh Kavir) at room temperature. UV-visible spectra
were acquired with a T60UV UV-VIS spectrophotometer.
Among the various types of MNPs, more atten-
tion has been paid to the Fe O nanoparticles because
3
4
2.2. Preparation of Fe O /Graphene
3
4
of their unique properties such as simple synthesis, inex-
pensiveness, low toxicity, biocompatibility, good super
paramagnetic property and having a very active surface
for adsorptions and immobilization of ligands, metals
and catalytic species [20–22]. On the other hand, due
Oxide Nanocomposite
Graphene oxide was prepared from graphite according to
the modified Hummers method [35, 36]. To synthesis of
the Fe O /Graphene oxide nanocomposite (with Fe O to
3
4
3
4
Graphene oxide mass ratio of 10) [37], Graphene oxide
(0.25 g) was dispersed in distilled water (30 mL). Then
ethanol (40 mL) was added and the mixture was sonicated
for 20 min. FeCl ·6H O (5.84 g 3.52 mmol) and FeCl ·
to their higher surface energy, Fe O nanoparticles may
3
4
rapidly aggregate and convert to bulkier form. So, to
overcome this drawback, improving the chemical stabil-
ity and also to achieve some advantages as the versatil-
ity in surface modification, this compound is generally
coated with various organic or inorganic materials and
recently graphene oxide [23].
3
2
2
4
H O (2.15 g, 3.78 mmol) were dissolved in 50 mL of dis-
2
tilled water under sonication. Then the solution was added
dropwise into the Graphene oxide suspension and stirred.
The obtained solution was slowly basified with aqueous
Graphene oxide, an attractive class of carbon-based
nanomaterial, is an excellent eco-friendly candidate for
NH OH (25%, 40 mL) up to pH∼10 and was heated
4
ꢀ
at 68 C for 2 h. Finally, the Fe O /Graphene oxide
3
4
protection of Fe O MNPs because of its exceptional prop-
3
4
nanocomposite was separated from the mixture using an
external magnet, washed three times with ethanol and dis-
tilled water respectively and dried at 65 C for 12 h.
erties such as mechanical stability, large surface area,
tunable electrical and optical properties [24]. Moreover,
the abundant of several types of oxygen-containing func-
tional groups including epoxy, hydroxyl groups and car-
ꢀ
2
.3. Preparation of Fe O /Graphene Oxide/Pr–NH
3 4 2
boxylic acids on the large surfaceI Pa r: e 9a 1 o. 2f 0G 0r. a8 p1h . e8 n1 e Oo xn i: d Me on, 30 Dec 2019 09:57:25
The obtained Fe O /Graphene oxide nanoparticles
3
4
Copyright: American Scientific Publishers
not only leads to excellent aqueous dispersity but also
(
3
2 g) were dispersed in EtOH (140 mL). Then,
-aminopropyltriethoxysilane (APTES) (4 mL) was added
Delivered by Ingenta
provide efficacious anchoring sites to immobilize desired
species and further chemical modifications [25–27]. On the
other hand, copper-based catalysts play an important role
in chemical transformations. In the last decade, a number
of copper-based catalytic systems have been used for the
conversion of the nitro group to amine [28–34]. Due to the
remarkable results of these studies and on the basis of
the above considerations, we were interested to investigate
and the mixture was sonicated for 1 h. After that, the
ꢀ
reaction mixture was stirred under N atmosphere (70 C,
2
2
0 h). The desired product was collected using a perma-
nent magnet, washed with distilled water and ethanol and
ꢀ
dried (60 C, a daytime).
2
.4. Preparation of Fe O /Graphene
3 4
II
the applicability of Fe O /Graphene oxide/Pr–NH –Cu as
II
3
4
2
Oxide/Pr–NH –Cu
2
a novel magnetically recoverable catalyst for the reduc-
tion of 4-nitrophenol to 4-aminophenol in the presence of
sodium borohydride.
Finally, for the preparation of Fe O /Graphene oxide/Pr–
3
4
II
NH –Cu , Cu(OAc) ·4H O (1 mmol) was added to a sus-
2
2
2
pension of Fe O /Graphene oxide/Pr–NH nanoparticles
3
4
2
(
1 g) in ethanol (25 mL). The mixture was refluxed for
2
. EXPERIMENTAL DETAILS
20 h. The final product (Fe O /Graphene oxide/Pr–NH –
3
4
2
II
2
.1. Materials and Methods
Cu ) was separated by permanent magnet, washed with
ꢀ
ethanol and dried at 50 C.
Highly pure Chemicals were purchased from Sigma-
Aldrich, Fluka and Merck Chemical Companies and used
without further purification. X-ray diffraction (XRD) mea-
surements were performed using Panalytical X’Pert Pro
instrument. Fourier transform infrared (FT-IR) spectra
were recorded on a Bruker Alfa FT-IR spectrometer using
pressed KBr pellets at room temperature. Morphology
and particle size were studied by field emission scan-
ning electron microscope (FE-SEM) (MIRA3 TESCAN).
The chemical composition of the catalyst was determined
using energy dispersive X-ray analyzer (EDX). Elemental
2.5. Catalytic Reduction of 4-Nitrophenol
To investigate the catalytic reduction of 4-nitrophenol,
NaBH (0.01 g) was added to a 20 ppm 4-nitrophenol
4
aqueous solution (20 mL). Then 0.01 g catalyst was added
and the mixture was allowed to stir at room temperature
until the deep yellow color of the solution turned color-
less. UV-Vis spectroscopy was used to monitor the reac-
tion progress. Upon completion of the reaction, the catalyst
was simply separated from the reaction mixture using a
122
J. Nanosci. Nanotechnol. 20, 121–127, 2020

Zabihzadeh et al.
Magnetic Fe O /Graphene Oxide/Copper-Based Nanocomposite as a Reusable Catalyst
3 4
permanent magnet, washed several times with ethanol and
deionized water and dried for the next cycle.
3
. RESULTS AND DISCUSSION
3
.1. Catalyst Characterization
The size and morphology of particles in the prepared cat-
alyst was evaluated using FE-SEM (Fig. 1). Based on this
technique the catalyst is as granule nanoparticles with the
size distribution ranged from 18–28 nm. The EDX spec-
trum of the catalyst is presented in Figure 2, which indi-
cated the presence of all of the expected elements (C, Fe,
O, Si, N, and Cu) and also confirms that copper (II) com-
plex was immobilized on the Fe O /Graphene oxide/Pr–
3
4
Figure 3. Magnetization curves of (a) Fe O /graphene oxide and
3
4
NH . The actual amount of Cu in prepared catalyst was
2
II
(
b) Fe O /graphene oxide/Pr–NH –Cu .
3
4
2
determined using inductively coupled plasma-optical emis-
sion spectrometry (ICP-OES). This analysis indicated that
the weight percentage of Cu was 6.3%.
X-ray diffraction (XRD) analysis was performed in
order to determine the phase structure of Fe O /Graphene
Figure 3 shows the magnetization hysteresis curves for
Fe O /Graphene oxide nanoparticles (curve a) and the syn-
3
4
II
oxide/Pr–NH –Cu (Fig. 4). In XRD analysis, the diffrac-
2
3
4
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
tion peaks at 2ꢀ = 30.31 , 35.67 , 43.28 , 53.75 , 57.30 ,
thesized catalyst (curve b). As can be seen, the satu-
ꢀ
and 62.93 can be indexed to (2 2 0), (3 1 1), (4 0 0),
ration magnetization (M ) of the Fe O /Graphene oxide
s
3
4
−
1
(4 2 2), (5 1 1) and (4 4 0) planes of Fe O -NPs in
nanoparticles was about 29.63 emu g , which decreased
to 26.92 emu g for Fe O /Graphene oxide/Pr–NH –Cu .
3
4
−1
II
the cubic phase (JCPDS 89-2355). The pure Graphene
oxide shows a sharp characteristic peak at 2ꢀ = 11.28
which can be attributed to the (0 0 1) plane of Graphene
oxide. However, no diffraction peak related to Graphene
oxide is observable for the obtained XRD spectrum
3
4
2
However, it was still large enough for magnetic separation.
Thus, after the end of the reaction, the catalyst could be
easily collected by a permanent magnetic from the reaction
medium.
IP: 91.200.81.81 On: Mon, 30 Dec 2019 09:57:25
II
of Fe O /Graphene oxide/Pr–NH –Cu , probably because
Copyright: American Scient
3
ific
4
Publishers
2
Delivered byt hI ne g lea ny te ar stacking of the Graphene oxide sheets were
destroyed by the loading of Fe O -NPs [37]. The average
3
4
nanoparticel diameter of the prepared catalyst was calcu-
lated about 12 nm from the XRD results using the Debye
Scherrer formula.
The FT-IR spectra of Fe O /Graphene oxide and
3
4
II
Fe O /Graphene oxide/Pr–NH –Cu
are shown in
3
4
2
Figure 5. These spectra show absorption bands at 443 and
−1
5
84 cm , which are attributed to the vibrational frequency
of Fe–O bond. In the case of Fe O /Graphene oxide,
3
4
II
Figure 1. FE-SEM image of Fe O /graphene oxide/Pr–NH –Cu .
3
4
2
II
II
Figure 2. EDX spectrum of Fe O /graphene oxide/Pr–NH –Cu .
Figure 4. The XRD pattern of Fe O /graphene oxide/Pr–NH –Cu .
3 4 2
3
4
2
J. Nanosci. Nanotechnol. 20, 121–127, 2020
123

Magnetic Fe O /Graphene Oxide/Copper-Based Nanocomposite as a Reusable Catalyst
Zabihzadeh et al.
3
4
Figure 6. UV-visible spectrum of the 4-nitrophenol aqueous solution.
Figure 5. FT-IR spectra of (a) Fe O /graphene oxide and
3
4
II
(
b) Fe O /graphene oxide/Pr–NH –Cu .
Cu–NH cannot be seen in the FT-IR spectrum because it
3
4
2
2
is covered by the Fe–O stretching vibrations [39].
−
1
the broad band observed at around 3400 cm is related
to the presence of hydroxyl groups of Graphene oxide
and Fe O . The absorption bands at 1180, 1402, 1618,
3
.2. Catalytic Activity
After synthesis and characterization of Fe O /Graphene
oxide/Pr–NH –Cu nanocomposite, its catalytic activity
was investigated in the reduction of 4-nitrophenol in the
presence of an excess amount of NaBH as the mild reduc-
ing agent in the aqueous solution (Scheme 1).
It is well documented that NaBH4 as the source
of hydrogen, does not reduce nitro group alone under ordi-
3
4
3
4
II
−1
2
and 1711 cm can be attributed to C–O (epoxy group),
C–OH (carboxyl group), C C, and C O stretching
vibrations (carboxyl group) of graphene oxide, respec-
tively. The addition of APTES to the Fe O /Graphene
4
3
4
oxide is confirmed by the new peaks at 2927, 2863, 1073
−1
and 1127 cm that are correspo nI Pd :t 9o 1t .h2 e0 0s y. 8m 1 m. 8e 1t r iOc na :n Md on, 30 Dec 2019 09:57:25
nary conditions [40] and requires to associate with an ade-
Copyright: American Scientific Publishers
asymmetric stretching vibrations of C–H bonds and Si–O
quate amount of catalyst. So, in order to demonstrate the
Delivered by Ingenta
stretching vibrations [38]. The presence of Cu(OAc) in
the catalyst is confirmed by the absorption bands at 1462,
581 and 1725 cm that are related to asymmetric and
2
necessity of using a catalytic system for the conversion
of 4-nitrophenol to 4-aminophenol, the reduction proce-
dure was conducted in the absence of the synthesized cat-
alyst at first. The chemical reduction of 4-nitrophenol was
easily studied using UV-Vis spectroscopy. As observed in
−1
1
symmetric stretching vibrations of acetate ions and C
O
−1
stretching vibration. The peak at 428 cm related to
II
Scheme 1. Preparation process and application of Fe O /Graphene oxide/Pr–NH –Cu in the reduction of 4-nitrophenol.
3
4
2
124
J. Nanosci. Nanotechnol. 20, 121–127, 2020

Zabihzadeh et al.
Magnetic Fe O /Graphene Oxide/Copper-Based Nanocomposite as a Reusable Catalyst
3 4
NO2
NO2
NH2
Table I. Comparison of various catalysts in the reduction of
-nitrophenol by NaBH4.
4
NaBH4
NaBH , Catalyst
4
Catalyst
loading
Conversion
time (min)
H O, r.t.
H O, r.t.
Entry
Catalyst
Ref.
2
2
OH
O
OH
1
2
3
Au/graphene hydrogel
Au@TpPa-1
Au–Ag bimetallic
NPs supported on
LDH
0.1 mg
20 mg
20 ꢂL, 1 mg
12
13
30
[42]
[43]
[15]
Scheme 2. The catalytic reduction of the 4-nitrophenol to 4-aminophen.
Figure 6, 4-nitrophenol aqueous solution shows a strong
absorption peak at 317 nm. Upon the addition of NaBH4,
the absorption shows red-shift to 400 nm with a color
change from pale yellow to dark yellow because of the for-
mation of 4-nitrophenolate ions under alkaline conditions.
The maximum absorption peak remained unchanged at
00 nm even after two days, which revealed the reduction
of 4-nitrophenol will not proceed only in the presence of
NaBH . However, after the addition of a suitable amount
of the Fe O /Graphene oxide/Pr–NH –Cu nanocompos-
4
5
Cu microspheres
Ag/KCC-1
5 mg
20 ꢂL,
18
8.5
[44]
[45]
−1
10 mg mL
6
7
Pd@HCS
3 mg
150 mg
5
10
[46]
[47]
Hypercross-linked
porous PS/IL
networks
4
8
9
Ni-PVAm/SBA-15
Fe O /graphene
12 mg
10 mg
85
4
[48]
[This work]
3
4
II
4
oxide/Pr–NH –Cu
2
II
3
4
2
ite to this solution, the peak at 400 nm gradually dropped
in intensity and a new peak related to the formation
of 4-aminophenol appeared as a shoulder at 300 nm
magnet, washed several times with ethyl acetate, dried and
reused for the consecutive runs. For this experiment, the
catalyst was reused at least for five consecutive runs with-
out significant change in its catalytic activity.
(
Scheme 2, Fig. 7). After about 4 min the whole peak at
00 nm disappeared and the yellow color of the solution
4
altered to colorless which shows the complete conversion
of 4-nitrophenol to 4-aminophenol.
The applicability and efficiency of the prepared cat-
alyst was compared with some other published works
In the catalytic reduction of 4-nitrophenol with NaBH
for the reduction of 4-nitrophenol by NaBH . As can be
4
II
4
II
in the presence of Fe O /Graphene oxide/Pr–NH –Cu ,
3
4
2
seen, Fe O /Graphene oxide/Pr–NH –Cu has an excel-
3
4
2
as an electron transfer procedure [41], at first, the
IP: 91.200.81.81 On: Mon,l e3 n0 t Dc ae t ca l y2 t0i c1 9a c 0t i9v :i 5t y7 :f 2o 5r the reduction of 4-nitrophenol to
-nitrophenol and BH ion are both a Cb so opr yb re i dg ho t n: At hme es rui cr -a n Scientific Publishers
−
4
4
4-aminophenol (Table I).
Delivered by Ingenta
face of the catalyst by ꢁ–ꢁ stacking interactions. After
−
that, an electron transfer process happens from BH4 to
4
. CONCLUSION
4
-nitrophenol ions. Finally, the 4-aminophenol was des-
In summary, we have reported the synthesis and char-
orbed from the surface of the catalyst.
acterization of a novel nanocomposite formulated as
The reusability of a catalyst is very worthwhile from the
viewpoint of green chemistry and commercial applications.
To evaluate this issue, after completion of the reaction,
monitored by UV-Vis spectroscopy, the catalyst was sep-
arated from the reaction medium simply by a permanent
II
Fe O /Graphene oxide/Pr–NH –Cu as an efficacious and
3
4
2
environmentally benign catalyst for the reduction of
-nitrophenol to 4-aminophenol with NaBH in aqueous
4
4
solution. The advantages of this catalytic system are ease
of preparation, short time of the reaction, high catalytic
activity and the use of commercially available, cheap
and eco-friendly materials. Also, the magnetic nature of
this catalyst allows its easy separation from the reaction
medium by an external magnet. The catalyst can be reused
five times without noticeable changes of its catalytic activ-
ity. This catalytic system may also be used in the reduction
of other toxic organic pollutants.
Acknowledgments: We are thankful to the Research
Council of the University of Guilan for the partial support
of this research.
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3
4
II
oxide/Pr–NH –Cu .
2
J. Nanosci. Nanotechnol. 20, 121–127, 2020
125

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