Gold nanoparticles anchored onto the magnetic poly(ionic-liquid) polymer as robust and recoverable catalyst for reduction of Nitroarenes

Article abstract of DOI:10.1002/aoc.3825

Gold nanoparticles supported on poly ionic-liquid magnetic nanoparticles (MNP@PIL@Au) were synthesized by reduction of HAuCl4 with sodium borohydride. The synthesized catalyst was characterized using by AAS, TEM, FT-IR, EDS, TGA and XRD techniques. The performance of the synthesized catalyst was investigated in the reduction of nitroarenes with NaBH₄. The reaction was carried out for various nitroarenes in water and mild conditions with high yields. The catalyst selectivity for the reduction of nitro group in the presences of other functional groups such as halides and alkynes was fairly well. The recycling of the catalyst was done 8 times without any significant loss of its catalytic activity.

Full text of DOI:10.1002/aoc.3825

Received: 6 December 2016
DOI: 10.1002/aoc.3825
Revised: 20 February 2017
Accepted: 6 March 2017
F U L L PA P E R
Gold nanoparticles anchored onto the magnetic poly(ionic‐liquid)
polymer as robust and recoverable catalyst for reduction of
Nitroarenes
Firouz Matloubi Moghaddam1
| Seyed Ebrahim Ayati1 | Hamid Reza Firouzi1 |
Seyed Hassan Hosseini2 | Ali Pourjavadi2
1 Department of Chemistry, Laboratory of
Organic Synthesis and Natural Products,
Sharif University of Technology, Azadi
Street, PO Box 111559516 Tehran, Iran
2 Department of Chemistry, Polymer
Research Laboratory, Sharif University of
Technology, Azadi Street, PO Box
111559516 Tehran, Iran
Gold nanoparticles supported on poly ionic‐liquid magnetic nanoparticles
(MNP@PIL@Au) were synthesized by reduction of HAuCl4 with sodium
borohydride. The synthesized catalyst was characterized using by AAS, TEM, FT‐
IR, EDS, TGA and XRD techniques. The performance of the synthesized catalyst
was investigated in the reduction of nitroarenes with NaBH4. The reaction was
carried out for various nitroarenes in water and mild conditions with high yields.
The catalyst selectivity for the reduction of nitro group in the presences of other
functional groups such as halides and alkynes was fairly well. The recycling of
the catalyst was done 8 times without any significant loss of its catalytic activity.
Correspondence
Firouz Matloubi Moghaddam, Sharif
University of Technology, Azadi Street, PO
Box 111559516, Tehran, Iran.
Email: matloubi@sharif.edu
KEYWORDS
gold nanoparticles, nitroarenes, poly(ionic‐liquid), reduction, water
1 | INTRODUCTION
organic transformations, reduction of nitro aromatic com-
pounds is of importance because they are significant interme-
Owning to unique chemical and physical properties of noble
metal nanoparticles (NPs) they are used in a wide range of
application and various fields.[1] Among the noble metals,
gold nanoparticles are the best because they not only have
extra catalyst properties, but also have a good biocompatibil-
ity and low toxicity.[2] The first report of gold catalytic activ-
ity in organic transformations was introduced by Hayashi and
co‐workers.[3] AS gold particlesare bulked sized, they have
no catalytic activity, and are known as an inert metal in
organic reactions. Thereforeafter the first synthesis of gold
nanoparticles and their application in selective hydrogena-
tion,they emerged as an excellent catalyst.[4] Gold (Ions and
NPs) have been used in oxidation of alcohols,[5] A3 coupling
reaction (synthesis of propargyl amines),[6] epoxydation of
alkenes[7] click reaction[8] C‐C bond formation,[9] cyclization
diate in analgesic and antipyretic drugs, photographic
development, corrosion inhibition,[14] anticorrosion lubrica-
tion, pharmaceuticals, polymers, herbicides and other fine
chemicals.[15] The nitro reduction has been done with differ-
ent catalysts such as copper nanorods,[16] nickel‐tin bimetal-
[17]
[19]
lic NPs,
microcrystalline SrBi2Nb2O9
Ru/MgLaO,[18] nanoparticles N‐doped TiO2,
and Ni nanocomposite.[21]
[20]
Because of high expenses of preparation of noble metal nano-
particles and its toxic effect on biological processes, the
recovery of metal NPs is strongly demanded. The anchoring
process is one of the best and most promising methods that
applied in organic reactions for the recovery of catalyst from
the reaction medium. Gold NPs have been supported on
Al2O3 [22], MgO, polymers, silica nanoparticles, TiO2,
CeO2, ZrO2, Cs2CO3, periodic mesoporous organosilicas,
nanocrystalline magnesium oxide and glutathione,[23] The
separation, losing activity, metal leaching and recovery of
the catalysts are the major challenges of the mentioned
supports. To overcome these problems, the immobilization
reactions,[10] deoxygenative coupling of nitroarenes to
[11]
synthesize aromatic azo compounds,
carbon‐heteroatom
bond forming reactions[12] and reduction of nitro com-
pounds[13] in the past decade. Among the aforementioned
Appl Organometal Chem. 2017;e3825.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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MOGHADDAM ET AL.
of catalyst on magnetic nanoparticles (Fe3O4) is one of the
best and most trusted methods that have been reported in
the literature during last decade. High thermal stability, easy
separation, low toxicity and high surface area are only a part
of benefits from the developments in this area.[24]
nanoparticles, Fe3O4@SiO2(MNPs) was reacted with 3‐
(trimethoxysilyl)propylmethacrylate (MPS). This part of cat-
alyst was named Fe3O4@SiO2@MPS(MNPs@MPS). In the
next step, for the synthesis of aforementioned catalyst,
MNPs@MPS, 1‐vinyl imidazole, 1‐ethyl‐3‐vinyl imidazolium
bromide and 1,4‐butanediyl‐3,3′‐bis‐1‐vinylimidazolium
dibromide, as a cross linker with the ratio 1/2.5/1/0.5, were
reacted in the presence of AIBN as an initiator. Due to the
polymer coating, the catalyst adsorbs more gold ions than tradi-
tional heterogeneous catalysts. Also, the polymer chains on the
surface of the catalyst increase the spacer length and the sub-
strates can easily adsorb onto the catalyst surface. Moreover,
the ionic part of the copolymer in the MNP@PIL structure
accelerates the substrate adsorption onto the catalyst surface
and the reaction proceeds faster. For the stabilization of gold
onto the PIL, a solution of HAuCl4 was added to the mixture
of PIL and then a solution of sodium borohydride immediately
was added to the mixture. The alteration of catalyst color from
yellow to purple is a powerful evidence for formation of gold
nanoparticles.[26]
The TGA (Thermogravimetric analysis) and DTG
(differential thermal gravimetric) analysis (Figure 1).of
catalyst show three picks at 100 °C, 320 °C and 390 °C
(sharp picks) that correspond to water evaporation and
degradation of immobilized polymer onto the magnetic nano-
particles, respectively. According to the TGA and DTG
curves, it could be concluded that not only an excellent
amount of polymer is loaded onto the MNPs but also the ther-
mal stability of catalyst is excellent.
Poly ionic liquids (PIL) offer unique potential as catalysts
and smart supports.[25] As it is well known, PILs are the
anchors with high surface area, high loading, low leaching
and are environmentally friendly. With this come the advan-
tages, PIL supported on the magnetic nanoparticles could
be an excellent anchor for the immobilization of metal nano-
particles. Here we are going to introduce a new gold nanopar-
ticles stabilized onto magnetic nanoparticles@poly‐ionic
liquid (MNPs@PIL). The catalyst have been synthesized in
our research group and have been used for the synthesis of
poropargylamines.[6] To investigate catalyst efficiency,
reduction of nitro aromatic compounds was selected as a
model reaction. The reaction was conducted under mild and
green conditions. The corresponding amines were obtained
with excellent yields and good selectivity in the reduction
and the presence of other functional groups. The catalyst
was used eight times without any significant activity loss.
The survey of catalyst properties and optimization of reaction
conditions have detailed are in results and discussion.
2 | RESULT AND DISCUSSION
The
schematic
preparation
of
magnetic
nanoparticles@polyionicliquid immobilized gold nanoparti-
cles is depicted in Scheme 1. At first step, for the preparation
of covalent bond between poly‐ ionic liquid and magnetic
The FT‐IR of magnetic nanoparticles functionalized
by polyionicliquid stabilized gold nanoparticles
(MNPs@PIL@AuNP) (d), MNPs@PIL (c), MNPs@MPS (b)
SCHEME 1 Synthesis of the catalyst

MOGHADDAM ET AL.
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FIGURE 1 TGA and DTG of MNPs@PIL
FIGURE 3 The EDS analysis of MNPs@PIL@AuNPs catalyst
FIGURE
2
FT‐IR spectra of MNPs (a), MNPs@MPS (b),
MNPs@PIL (c) and MNPs@PIL@AuNPs catalyst (d)
and MNPsare depicted in Figure 2. The peaks at 640 cm‐1 and
1100 cm‐1 are indication of the stretchingvibration mode of
Fe–O and Si–O that confirms the formation of MNPs
(Figure 2a). The presence of peaks at 1420 and 1720 cm‐1 that
belongs to the stretching mode vibrations of C = C and steric
C = O are logical reasons for bond formation between
MNPs@MPS (Figure 2b). The anchored poly‐ionic‐liquids
onto the MNPs leads to appearance of peaks at 3100, 1610
and 1530 cm‐1respectively (Figure 2c). The stabilization of
gold nanoparticles did not result in appearance of the new
peaks at Mid‐IR (Figure 2d).
The EDS analysis of the synthesized catalyst proved high
levels of absorbed gold nanoparticles onto the polymer. The
iron and silicon peaks of the catalyst that can be attributed
to MNPs@MPS, clearly prove the presence of magnetic
nanoparticles in the catalyst's matrix (Figure 3).In the subse-
quent analysis atomic absorption spectroscopy (AAS) was
used as a powerful tool for the measurement of the amount
of stabilized gold onto the MNPs@PIL. These results clearly
support that good level (1.94 mmolg‐1) of gold was loaded
onto the MNP@PIL matrix.
FIGURE 4 The XRD pattern of MNPs@PIL@AuNPs (a) and
magnetization curves of MNPs (I) and MNPs@PIL@AuNPs (II) (b)
nanoparticles with the indices peaks[27] prove that the
modifications did not affect crystalline structure of Fe3O4
and gold particles. The broad peak that is located at 2 theta
of around 20° could be attribute to the amorphous silica shell
around the magnetic nanoparticles. In another analysis, the
magnetization of MNP and MNPs@PIL were examined.
We envisioned that the magnetization power of
MNPs@PILsignificantly decreases in comparison with
MNP, but it is still enough to respond to an external magnetic
field (Figure 4b).
TEM image of MNPs@PIL@AuNPs provided us accu-
rate information about the morphology and particle size of
immobilizedgold nanoparticles onto the support. As depicted
The XRD pattern of MNPs@PIL@AuNPis shown in
Figure 4a. The comparison of Fe3O4peaks and gold

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MOGHADDAM ET AL.
FIGURE 5 The TEM image of MNPs@PIL@AuNPs and size histogram of magnetic nanoparticles
in Figure 5, the TEM image of MNPs@PIL@AuNPs indi-
cates a fairly good dispersion of gold nanoparticles on the
synthesized MNP@PIL matrix with the average size around
20 nm (a range size between 10 to 40 nm).
With this promising observation, the reduction of nitro
aromatic compounds was chosen as a model for investigation
of the synthesized catalyst activity. In the first reaction, the
reduction of p‐nitro phenol (1.0 mmol) in the presence of
sodium borohydride 10 (mmol) as a reducing agent and
1 mol % of catalyst were followed by ultra violet spectroscopy
(UV)(Figure6).andthinlayerchromatography(TLC)inwater,
at room temperature (Table 1, entry 3). Surprisingly the reac-
tion was completed just in 10 minutes and the corresponding
amine was obtained without any byproduct. To investigate the
effect of catalyst, the reaction was conducted in the absence of
FIGURE 6 UV–visible absorption spectra for the reduction of 4‐
nitrophenol over MNPs@PIL@AuNPs
TABLE 1 Reduction of 4‐Nitrophenol in the presence of MNPs@PIL@AuNPs under different reaction conditions in watera
Entry
Catalyst
Amount of catalyst
(mol%)
Amount of NaBH4 (mmol)
Time (min)
Yield (%)b
TON
TOF(h−1
)
1c
2c
3
‐
‐
20
20
10
20
30
40
7.5
5
120
120
10
8
n.d
<10
98
‐
‐
MNPs@PIL
‐
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
MNPs@PIL@AuNPs
1
98
588
735
840
1176
285
186
147
468
512
380
558
4
1
98
98
5
1
7
98
98
6
1
5
98
98
7
1
20
30
6
95
95
8
1
93
93
9
2
20
20
20
20
20
98
49
10
11
12
13
2.5
0.75
0.5
0.1
5
98
39
15
30
100
96
128
190
930
95
93
aCondition: 4‐Nitrophenol (1 eq.) in 5 mLs H2O at r.t.
bIsolated yield
cThe reaction in the absence of catalyst.

MOGHADDAM ET AL.
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TABLE 2 Reduction of nitroarenes by NaBH4 in the presence of MNPs@PIL@AuNPs in water (NaBH4/ nitro compound: 10:1, at room tem-
perature)a
Entry
1
Nitroarene
Product
Time (min)
10
Yield (%)b
98
2
3
70
40
96
98
4c
30
95
95
5c
100
6
7
8
25
60
15
93
95
94
9
10
35
97
95
10c
11
12
90
85
86
80
(Continues)

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MOGHADDAM ET AL.
TABLE 2 (Continued)
13
14
45
55
91
92
15
45
90
16
17
18
40
35
45
94
95
94
aCondition: Nitroarene (1 eq.), NaBH4 (10 eq.), MNPs@PIL@AuNPs (5 mg, 1.0 mol% Au) in 5 mLs H2O at room temperature.
bIsolated yield
cThe ratio of nitrioarene to NaBH4 is 1:20
catalyst and in the presence of MNPs@PIL (without gold
nanparticles). However, no considerable amount of amine
was obtained even after 2 h. To obtain the minimum ratio of
NaBH4 to nitro arenes, different amounts (mmol) of reducing
agent was used at the same conditions (Table 1, entries 4–8).
According to obtained results, the third entry was chosen
as the optimized amount for NaBH4. For optimizing the
amount of catalyst, the following mol% was used: 1, 2, 2.5,
0.75, 0.5 and 0.1 mol% (Table 1, entries 3, 9–13). As can
be seen, by decreasing the amount of catalyst, the reaction
time increases significantly (Table 1, entries 12, 13). In
contrast, increasing the catalyst amount, improves the yields
at the short times (Table 1, entries 9, 10). Because oxygen
has direct effect on reaction yields (cause to produce by
products), the reactions was followed under an inert
atmosphere.
FIGURE 7 Reuse of MNPs@PIL@AuNPs in reduction of 4‐
Nitrophenol

MOGHADDAM ET AL.
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TABLE 3 The comparison of MNPs@PIL@AuNPs with reported catalysts in the reduction of 4‐nitrophenol
Gold
Catalyst loading
(mol%)
Time
(min)
T
(°C)
Yield
(%)
Catalyst
Loading on catalyst (mmol/g)
Ref
[29]
[30]
[31]
[13]
Mesoporous TiO2@AuNPs
Mesoporous au–TiO2
Graphene oxide@AuNPs
MgO@ AuNPs
0.106
0.104
‐
1
60
120
30
7
r.t
r.t
r.t
r.t
r.t
99
94
2
5
15(mg)
1
98
0.07
1.94
100
98
MNPs@PIL@AuNPs
10
Present work
According to the obtained data, entry 3 was selected as
the best conditions for this reaction. After getting the optimal
conditions for reduction, the catalyst was checked for other
nitroarenes. Table 2 illustrates the reduction of nitroarenes
derivatives under optimized conditions. The reduction was
selective with high yields for halo nitroarenes (Table 2,
entries 5, 6, 13, 14). On the other hand the reduction of
carbonyl nitroarenes was done with over hydrogenation of
carbonyl group (Table 2, entry 15). In alkyne nitroarene
and alkene nitroarene, the reduction was completed without
affecting the alkyne and alkene functional groups (Table 2,
entries 16–18).
The activity of MNPs@PIL@AuNPs catalyst after
recycling was carried out using 4‐nitro phenol (Figure 7).
The catalyst was recovered after each cycle by an external
magnetic field and washed with a 50:50 mixture of water
and EtOH and finally dried at oven. The mentioned cycle
was repeated 8 times without any significant loss of catalyst
activity (Figure 7).
The metal leaching was also tested by atomic absorption
spectroscopy (AAS). AAS analysis indicated that there is
no significant gold leaching after 8 runs. With this promis-
ing observation, the proposed catalyst has an excellent
reactivity for the reduction of nitroarenes and good stability
for reusing.
A comparison between MNPs@PIL@AuNPs and other
reported supported gold catalysts is presented at Table 3.
As shown in Table 3, gold loading in MNPs@PIL@AuNPs
is higher than other catalysts due to imidazole groups
strongly adsorb gold ions from the solution. Also, the amount
of applied catalyst in the reaction was mostly lower than other
catalysts. These results show that the presence catalyst has
some advantage than other reported gold catalysts.
was used for the reduction of nitroarenes. The reaction is sim-
ple and followed under green and mild conditions. Reduction
of halo nitroarenes under MNPs@PIL@AuNPs was done
without over hydrogenation. The simple synthesis, easy mag-
netic recovery, excellent reusability (up to 8 runs) and high
loading of gold nanoparticles on the catalyst surface are some
of advantages of the present catalyst which make it useful in
large scale application.
4 | EXPERIMENTAL SECTION
4.1 | General
Ferric chloride hexahydrate (FeCl3.6H2O), ferrous chloride
tetrahydrate (FeCl2.4H2O), tetrachloroauric(III) acid
trihydrate
(HAuCl4),
ammonia
(30%),
and
3‐
methacryloxypropyltrimethoxy silane (MPS, 98%) were pur-
chased from Merck. 1‐Vinylimidazole was obtained from
Aldrich and it was distilled before use. 1,4‐Dibromobutane
was obtained from Aldrich, while the 2,2′‐azobisisobutyronitrile
(AIBN, Kanto, 97%) was recrystallized from ethanol.
FTIR spectra of samples were recorded by using an ABB
Bomem MB‐100 FTIR spectrophotometer. Thermogravimet-
ric analysis (TGA) was performed under the nitrogen atmo-
sphere using a TGA Q 50 thermogravimetric analyser. The
morphology of the catalyst was investigated by using a
Philips XL30 scanning electron microscope (SEM) and trans-
mission electron microscopy (TEM) images were taken by
using a Philips CM30 electron microscope.
4.2 | Synthesis of vinyl functionalized
magnetic nanoparticles
Fe3O4 magnetic nanoparticles (denoted as MNPs) were syn-
thesized by a co‐precipitation method and coated by silica
according to previous works.[28] A suspension of MNPs
was prepared by dispersion of 1 g Fe3O4@SiO2 in dry etha-
nol. After adding 2 ml of ammonia solution to the flask, an
excess amount (10 mmol) of the 3‐(trimethoxysilyl)
propylmethacrylate (MPS) solution was gradually added to
the mixture. The mixture allowed to stir at 60 °C for 48 h.
3 | CONCLUSION
In this study a new heterogeneous catalyst based on gold
nanoparticles stabilized on magnetic poly(imidazole/
imidazolium), with excellent stability in aqueous solution
and air, was prepared through a simple procedure and it

8 of 9
MOGHADDAM ET AL.
The MPS coated magnetic nanoparticles (denoted as
MNPs@MPS) were collected using an external magnetic
field. The product was washed with methanol 5 times and
dried under vacuum oven at 50 °C for 24 h.
4.5 | General procedure for the synthesis of
aromatic amines
A proper flask was charged with deionized water (5 ml). 4‐
nitrophenol (1 mmol) is dissolved in water and 10 mmol of
NaBH4 is added to the solution and stirred till a homoge-
neous solution is obtained. The solution is degassed with
N2 for 10 minutes. Then 5 mg of MNPs@PIL@AuNPs cata-
lyst was added and stirring continued. The reaction comple-
tion was followed by thin layer chromatography (TLC)
(EtOAc/ n‐hexane, 20:80). In each case, after completion,
the product was worked up and purified. Briefly, the working
up and purification procedure was as follows.More purifica-
tion was done by SiO2 column chromatography. In order to
reuse the catalyst, the catalyst (MNPs@PILAu) was collected
using an external magnetic field, washed with methanol and
dried under vacuum at 50 °C for 10 h for the next run.
4.3 | Synthesis of IL monomer and cross‐
linker
For the synthesis of ionic liquid (IL) as a common method, a
mixture of 1‐vinylimidazole (2.82 g, 30 mmol) and ethyl bro-
mide (3.27 g, 30 mmol) allowed to stir in 10 ml of methanol
at 60 °C for 20 h. The mixture was then cooled down to room
temperature and gradually added to 250 ml of diethyl ether.
The resulting semi‐transparent mixture was cooled down to
−10 °C and then allowed to stand at that temperature for
5 h. The white solid was filtered through sintered glass and
washed with diethyl ether three times. The product was
dried under vacuum at 50 °C. The same procedure was
used for the synthesis of 1,4‐butanediyl‐3,3′‐bis‐1‐
vinylimidazolium bromide.
ACKNOWLEDGMENTS
We gratefully acknowledge the funding support received for
this project from the Sharif University of Technology
(SUT), Islamic Republic of Iran.
4.4 | Synthesis of the catalyst
REFERENCES
The catalyst was previously synthesized by our research
group [25b]. A mixture containing MNsP@MPS (0.4 g), 1‐
vinylimidazole (Vim, 1 g), IL monomer ([EVim][Br],
0.4 g), cross‐linker ([BBVim][Br]2, 0.2 g) and 30 ml of dry
methanol was sonicated for 20 min. The reaction mixture
was then degassed by bubbling with argon for 10 min. A cer-
tain amount of AIBN (0.1 g) was added to the mixture of
reaction, and then the flask was equipped with a condenser
and placed in an oil bath for 18 h at 70 °C. The produced poly
imidazole‐ imidazolium bromide magnetic nanoparticles
(MNPs@PIL) were collected using an external magnetic
field. The product was washed with methanol 3 times and
dried under vacuum oven at 50 °C (MNPs@PIL, 1.37 g).
Tetrachloroauric(III) acid trihydrate (0.1 g) was dissolved in
30 ml of deionized water. The powdered magnetic PIL
(0.5 g) was then added, and the mixture allowed to stir at
room temperature for 5 h. After separating the catalyst
(MNPs@PILAu) by magnetic field, it was washed with
methanol (4 × 10 ml) 4 times and dried under vacuum at
40 °C for 10 h.The resulted yellow solid which is
MNP@PILAu dispersed in a 50:50 solution of H2O/MeOH
and stirred at room temperature. A solution of 0.2 g NaBH4
in 1 ml of deionized water is added to the mentioned mixture.
The appearance of red win color in solution is a reason for the
formation of gold nanoparticles onto the ionic liquid
polymer. The MNPs@PIL@AuNPs were collected using an
external magnetic field and washed with methanol 5 times
and dried under vacuum oven at 50 °C for 24 h.
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How to cite this article: Moghaddam FM, Ayati SE,
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