Immobilization of Au nanoparticles on poly(glycidyl methacrylate)-functionalized magnetic nanoparticles for enhanced catalytic application in the reduction of nitroarenes and Suzuki reaction

Article abstract of DOI:10.1002/aoc.5828

We report a novel strategy for the synthesis of magnetic nanocomposite for highly efficient catalysis. Poly(glycidyl methacrylate) (PGMA) chains were grafted to the surface of magnetic nanoparticles (MNPs) through surface-initiated reversible addition-fragmentation chain transfer polymerization. Then, the oxirane rings in the PGMA chains were opened with 2,6-diamino pyridine (DAP) molecules as ligands to prepare the solid support. Finally, this magnetic nanocomposite was used for the immobilization of gold nanoparticles. Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, gel permeation chromatography, vibrating sample magnetometry, and atomic absorption spectroscopy were used for characterization of the catalyst. The loading of gold nanoparticles on the solid support was 0.52 mmol/g. The catalytic activity of the prepared catalyst (MNP@PGMA@DAP@Au) was evaluated for the reduction of nitro compounds and C–C coupling reaction in water. The catalyst can be easily recovered and reused seven times without significant loss of catalytic activity.

Full text of DOI:10.1002/aoc.5828

Received: 8 January 2020
DOI: 10.1002/aoc.5828
Revised: 5 May 2020
Accepted: 5 May 2020
F U L L P A P E R
Immobilization of Au nanoparticles on poly(glycidyl
methacrylate)-functionalized magnetic nanoparticles for
enhanced catalytic application in the reduction of
nitroarenes and Suzuki reaction
Ali Pourjavadi
| Mohammad Kohestanian | Nahid Keshavarzi
Polymer Research Laboratory,
We report a novel strategy for the synthesis of magnetic nanocomposite for
highly efficient catalysis. Poly(glycidyl methacrylate) (PGMA) chains were
grafted to the surface of magnetic nanoparticles (MNPs) through surface-
initiated reversible addition-fragmentation chain transfer polymerization.
Then, the oxirane rings in the PGMA chains were opened with 2,6-diamino
pyridine (DAP) molecules as ligands to prepare the solid support. Finally, this
magnetic nanocomposite was used for the immobilization of gold
nanoparticles. Fourier-transform infrared spectroscopy, X-ray diffraction, ther-
mogravimetric analysis, transmission electron microscopy, scanning electron
microscopy, gel permeation chromatography, vibrating sample magnetometry,
and atomic absorption spectroscopy were used for characterization of the cata-
lyst. The loading of gold nanoparticles on the solid support was
0.52 mmol/g. The catalytic activity of the prepared catalyst
(MNP@PGMA@DAP@Au) was evaluated for the reduction of nitro com-
pounds and C–C coupling reaction in water. The catalyst can be easily recov-
ered and reused seven times without significant loss of catalytic activity.
Department of Chemistry, Sharif
University of Technology, Tehran, Iran
Correspondence
Ali Pourjavadi, Polymer Research
Laboratory, Department of Chemistry,
Sharif University of Technology,
Tehran, Iran.
Email: purjavad@sharif.edu
K E Y W O R D S
Au nanoparticles, heterogeneous catalysts, RAFT polymerization, reduction, Suzuki reaction
1 | INTRODUCTION
hydrogenation because this method has various advan-
tages such as mild condition, high yield of product
Reduction of nitroarenes is one of the most important
methods for the synthesis of aromatic amines.[1-4] Aro-
matic amines are widely used in the manufacture of
pharmaceuticals, photographic chemicals, agrochemi-
cals, polymers, and dyes.[5-7] In addition, the amine
group can be converted to diazonium salts and then
be easily replaced by other groups (H, F, Cl, Br, I,
OH, etc.).[2] There are numerous protocols for the
reduction of aromatic nitro compounds in the litera-
ture.[8-12] The most suitable method for the reduction
of nitro compounds is transition metal-catalyzed
and short reaction time. However, the recyclability and
recovery of the expensive metal catalyst at the end of
the reaction is very difficult. These drawbacks can be
overcome by immobilization of metal catalysts on solid
supports. Different kinds of metal catalysts such as Pd,
Pt, Fe, Cu, Au, and Rh have been immobilized on
solid supports and used for the reduction of nitro com-
pounds with various hydrogen sources.[13-15]
Suzuki–Miyaura is an important and powerful
approach to the construction of unsymmetrical biaryl
compounds.[16-19] Biaryl compounds are an important
Appl Organomet Chem. 2020;e5828.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
1 of 15
https://doi.org/10.1002/aoc.5828

2 of 15
POURJAVADI ET AL.
class of materials that have applications in pharmaceuti-
cals, advanced material chemistry, and agrochemi-
cals.[20-22] The Suzuki–Miyaura reaction is usually
performed by palladium catalyst.[23-26] Ni and Cu cata-
lysts have also been used for this reaction but they have
low yields.[27,28] Au catalysts have also exhibited high cat-
alytic activity in the Suzuki reaction.[29,30] However,
many reports have been developed for the Suzuki–
Miyaura cross-coupling reaction using gold nanoparticle
catalysts.[31]
Using a homogeneous Au catalyst for reduction of
nitro compounds and the C–C coupling reaction has
several drawbacks, such as limited reusability and
recyclability, deactivation, and instability of the cata-
lyst.[32-35] Heterogenization of the homogeneous cata-
advantage of the RAFT technique, magnetic behavior, and
Au nanoparticles in the synthesis of a novel catalyst.
Herein, a novel magnetic nanocomposite was synthe-
sized and utilized as solid support for the immobilization of
Au nanoparticles. First, 2-(dodecylthiocarbonothioylthio)-
2-methylpropionic acid (DDMAT) was attached to the sur-
face of MNP@SiO2 and then polymeric shell (poly(glycidyl
methacrylate) [PGMA] chains) were attached from the sur-
face of MNP@SiO2 through the SI-RAFT approach. The
oxirane rings in the polymeric shell (PGMA shell) are active
groups that can be reacted with various groups such as –
OH, –NH2, and –COOH.[63,64] Afterwards, the 2,6-
diaminopyridine (DAP)-functionalized MNP@PGMA was
prepared through a ring-opening reaction between oxirane
groups of PGMA chains and amine groups of the DAP moi-
ety (MNP@PGMA@DAP). Au nanoparticles (Au NPs)
were immobilized on DAP-modified nanoparticles to form
the catalyst. Under green media, the prepared catalyst
exhibits high catalytic efficiency in nitroarene reduction
and the Suzuki–Miyaura coupling reaction, as well as easy
separation and recyclability under an external magnetic
field.
lyst is
a
versatile approach to overcome these
problems. Various solid materials such as TiO2,[36-38]
polymers,[39-41] mesoporous organosilicas,[42,43] magne-
sium oxide, and magnetic nanoparticles[44–46] have
been used as support for the immobilization of gold
ions and nanoparticles. Among various support mate-
rials, polymer-grafted magnetic nanoparticles are very
attractive since they demonstrate unique properties
such as high activity, easy recyclability, and easy sepa-
ration. There are many methods for the synthesis of
polymer-attached solid surfaces such as atom transfer
radical polymerization (ATRP) and reversible addition-
fragmentation chain transfer (RAFT). In the past
decade, the surface-initiated reversible addition-
fragmentation chain transfer (SI-RAFT) method has
been widely used for the preparation of polymer
chains grafted onto various solid surfaces such as
graphene oxide,[47–50] TiO2,[51,52] Fe3O4,[53–55] and sil-
ica.[56,57] Recently, the surface-grafting of a polymeric
layer to various types of nanoparticles by the SI-RAFT
approach has attracted interest because of its applica-
tions in catalysis,[58] drug delivery systems,[47,59]
sensors,[57] electronics, and coatings.[60]
2 | EXPERIMENTAL
Glycidyl methacrylate (GMA, 97%) was obtained from
Sigma-Aldrich and distilled under vacuum before use.
DDMAT as RAFT agent was synthesized as reported pre-
viously.[59] Ferric chloride hexahydrate (FeCl3.6H2O), fer-
rous chloride tetrahydrate (FeCl2.4H2O), (3-aminopropyl)
triethoxysilane (APTS), methyltrioctyl ammonium chlo-
ride, azobis(isobutyronitrile) (AIBN), hydrochloric acid,
DAP, tetraethyl orthosilicate (TEOS), ammonium
hydroxide (NH3.H2O, 25%), and tetrachloroauric(III) acid
trihydrate (AuHCl4.3H2O) were purchased from Sigma-
Aldrich. All solvents and other reagents were obtained
from Merck (Germany).
Dongmei et al. functionalized magnetic graphene
oxide with poly(NIPAM-co-ETMA) via RAFT polymeri-
zation for reduction of nitrophenols.[58] Chen and co-
workers have also reported the successful synthesis of
thermosensitive GO@poly(NIPAM) by surface-initiated
RAFT polymerization for nitrophenol reduction.[61]
Ghasemi and co-workers reported the successful
modification of silica nanoparticles with polyacrylamide
chains via the RAFT approach and used them as solid
support for the catalyst in Heck reactions.[62]
Until now, to the best of our knowledge, polymeric
chains grafted on magnetic nanocomposite (MNP) via the
SI-RAFT approach have not been fully investigated for cat-
alytic application, so it is really demanding and promising
to develop such systems. In this study, we combine the
2.1 | Characterization
Fourier-transform infrared (FT-IR) spectra were obtained
in the range of 400–4,000 cm−1 on an ABB Bommem
MB-100 spectrophotometer (Canada) using potassium
bromide pellets. The amount of gold in the supported cat-
alyst was determined by atomic absorption spectroscopy
(AAS, Shimadzu 680A, Kyoto, Japan). Thin layer chro-
matography (TLC) was performed with silica gel 60 F254
plates. NMR spectra were recorded on a Bruker NMR
500 MHz spectrometer (Netherlands) in chloroform
(CDCl3) and dimethylsulfoxide (DMSO). Ther-
mogravimetric analysis (TGA) was performed at a

POURJAVADI ET AL.
3 of 15
heating rate of 10ꢀC per min under N2 flow over a tem-
perature range of 25–900ꢀC using a TGA Q 50 instrument
(Canada). Transmission electron microscopy (TEM) on a
Philips CM30 (Netherlands) transmission electron micro-
scope with an accelerating voltage of 100 kV was used to
study the samples. The surface morphology of the cata-
lyst was observed using a Mira3 Tescan scanning electron
microscope (SEM) (Czech Republic). X-ray diffraction
(XRD) patterns were recorded by Rigaku D/Max-3c
(Japan) with Cu kα radiation in the 2θ range of 5–80ꢀ at
room temperature. GPC measurement was made on a
GPC Agilent 1,100 (United States) at 30ꢀC using tetrahy-
drofuran (THF) as eluent. Monodispersed polystyrenes
(PSs) were used as standards for calibration. The magne-
tization measurement was carried out in a vibrating sam-
ple magnetometer (Meghnatis Daghigh Kavir Co.,
Kashan, Iran).
added at 0ꢀC and the mixture was stirred at this tempera-
ture for 1 hr and then at room temperature for 24 hr. The
prepared DDMAT-functionalized MNPs were magneti-
cally collected, thoroughly washed several times with
DMF and methanol, and dried at 50ꢀC under low
pressure.
TGA analysis illustrated that the content of the RAFT
agent (DDMAT) immobilized to the surface of MNP is
0.247 mmol per gram.
2.4 | Preparation of MNP@PGMA
nanoparticles
First, 0.3 g of DDMAT-functionalized MNP was ultrasoni-
cally dispersed in 15 ml of anhydrous DMF for 40 min
and then the solution was cooled in an ice bath at 0ꢀC.
Then 4 ml of glycidyl methacrylate, 36 mg of DDMAT,
and 8.2 mg of AIBN were added and the flask was
degassed with argon for 20 min. RAFT polymerization
was performed at 75ꢀC. After 48 hr, the obtained
MNP@PGMA nanocomposites were magnetically col-
lected, washed three times with THF and ethyl acetate,
2.2 | Synthesis of modified magnetic
nanoparticles (MNP@SiO2@APTS)
The magnetic nanoparticles were synthesized by mixing
23.3 g (86 mmol) of FeCl3.6H2O and 8.6 g (43 mmol) of
FeCl2.4H2O in 500 ml of deionized water under a nitro-
gen atmosphere. Then 100 ml (25%) of concentrated
ammonia solution was added dropwise to the mixture at
50ꢀC. After 1 hr, the black precipitate was separated and
washed several times with ethanol and dried at 60ꢀC. To
prepare MNP@SiO2, 3 g of Fe3O4 nanoparticles were
suspended in 400 ml of ethanol/water mixture (4:1), and
the pH of the solution was adjusted to 11 by the addition
of NH3 solution. Then 15 ml of tetraethyl orthosilicate
(TEOS) was added dropwise to the solution and the mix-
ture was stirred at 50ꢀC for 6 hr. The prepared MNPs
(Fe3O4@SiO2) were magnetically separated and washed
several times with ethanol and dried at 50ꢀC. For the
preparation of MNP@SiO2@APTS, 2 g of MNPs was dis-
persed in 60 ml of toluene and sonicated for 20 min.
Then 4 ml of APTS was added dropwise and the mixture
was refluxed at 50ꢀC for 24 hr. The final product
(MNP@SiO2@APTS) was magnetically separated,
washed several times with ethanol, and dried at 110ꢀC
for 24 hr.
1
and dried at 60ꢀC at low pressure. The FT-IR and H
NMR spectra of the free polymer are shown in Supporting
Information Figures S1 and S2, respectively. The molecu-
lar weight of the free PNG is calculated to be about
22,600 g/mol, which is comparable to the value deter-
mined by GPC for free PNG (Mn = 23,800 g/mol, PDI
(Mw/Mn) = 1.36) (Supporting Information Figure S3).
2.5 | Synthesis of catalyst (MNP@
PGMA@DAP@au)
MNP@PGMA nanoparticles (0.4 g) were ultrasonically
dispersed in anhydrous toluene (15 ml) for 30 min. A
solution of 0.5 g of DAP and 5 ml of toluene was added to
the flask. The ring-opening reaction was performed for
24 hr at room temperature and then 24 hr at 70ꢀC with
stirring. The obtaining MNP@PGMA@DAP was magnet-
ically collected, washed three times with methanol, and
dried at 50ꢀC under vacuum.
To
synthesize
magnetic
nanocatalyst
(MNP@PGMA@DAP@Au), 0.3 g of MNP@PGMA@DAP
was ultrasonically dispersed in 30 ml deionized water
for 20 min. Then, a solution of AuHCl4 (1 ml, 0.2 M)
was added and the mixture was stirred for 24 hr at room
temperature. The resulting MNP@PGMA@DAP@Au III)
particles were magnetically separated and washed several
times with deionized water then were redispersed
in deionized water and 0.3 g of NaBH4 was added
to reduce Au(III) to Au(0). The mixture was stirred
2.3 | Synthesis of
MNP@SiO2@APTS@DDMAT
MNP@SiO2@APTS (0.3 g) was ultrasonically dispersed
in 50 ml of anhydrous DMF for 30 min. Subsequently,
DDMAT (0.9 g), dicyclohexylcarbodiimide (DCC, 0.45 g),
and 4-(dimethylamino) pyridine (DMAP, 0.2 g) were

4 of 15
POURJAVADI ET AL.
for 2 hr at room temperature. The final catalyst
(MNP@PGMA@DAP@Au) was magnetically separated,
washed several times with deionized water and methanol,
and dried at 60ꢀC under vacuum.
2.7 | General procedure for Suzuki–
Miyaura cross-coupling reaction catalyzed
by MNP@ PGMA@DAP@Au
A mixture of aryl halide (1 mmol), phenylboronic acid
(1.5 mmol, 0.182 g), K2CO3 (2 mmol, 0.276 g), and H2O
(4 ml) was added in a 25-ml round-bottomed flask and
MNP@PGMA@DAP@Au (0.5 mol%) was added. The
mixture was stirred at 60ꢀC. The progress of the reaction
was monitored by TLC. After completion of the reaction,
20 ml of ethyl acetate was added to the mixture and the
catalyst was separated with a magnet, washed with meth-
anol, and dried at 60ꢀC for next steps. The reaction mix-
ture was extracted with ethyl acetate and dried over
anhydrous MgSO4. The products were purified using a
silica gel column.
2.6 | General procedure for reduction of
nitroarenes catalyzed by MNP@
PGMA@DAP@Au
Different nitroarenes (0.5 mmol) were added to 4 ml
of deionized water in a 25-ml round-bottomed flask.
Then,
NaBH4
(2
mmol,
0.075
g)
and
MNP@PGMA@DAP@Au (0.3 mol%) were added. The
mixture was stirred under nitrogen for 20 min and
then stirred for an appropriate time at room tempera-
ture. The progress of the reaction was monitored by
TLC. After completion of the reaction, the catalyst was
magnetically separated, washed several times with
methanol, and dried at 60ꢀC for next steps. The reac-
tion mixture was extracted with ethyl acetate and dried
over anhydrous MgSO4. The products were purified
using silica gel plates.
3 | RESULTS AND DISCUSSION
3.1 | Preparation of the catalyst
Scheme
1 shows the synthesis of the magnetic
nanocomposite via RAFT polymerization. In the first
SCHEME 1 Synthetic route for MNP@PGMA@DAP@Au catalyst

POURJAVADI ET AL.
5 of 15
step, MNP was prepared by coprecipitation of Fe2+ and
Fe3+ salts in basic medium. The surface of the MNP was
modified by tetraethyl orthosilicate and then
functionalized with APTS to incorporate –NH2 groups on
the surface. Amine groups of amino-silane functionalized
MNP can react with carboxyl groups of the RAFT agent
by an amidification reaction at 25ꢀC. RAFT-
functionalized MNP was then used for RAFT polymeriza-
tion of GMA monomer, which was conducted in THF at
60ꢀC using AIBN as the initiator. In the next step, the
oxirane rings in MNP@PGMA were modified with DAP
molecules to prepare solid support. Gold(III) ions were
immobilized on MNP@PGMA@DAP by forming a com-
plex with amine functional groups and were then
reduced
to
gold
nanoparticles
to
prepare
MNP@PGMA@DAP@Au as the final catalyst. The pres-
ence of DAP in the structure of the catalyst leads to high
loading and low leaching of gold ions on the surface of
the catalyst.
The
FT-IR
spectra
of
MNP@SiO2,
MNP@SiO2@APTS,
MNP@SiO2@APTS@DDMAT,
MNP@PGMA, and MNP@PGMA@DAP are shown in
Figure 1. The FT-IR spectrum of MNP@SiO2 (Figure 1a)
shows absorbance peaks at about 576, 1,087, and
3,414 cm–1 corresponding to the stretching vibrations of
Fe–O, Si–O, and O–H, respectively. A weak absorbance
peak at 2924 cm–1 in the spectrum of MNP@SiO2@APTS
(Figure 1b) is attributed to the stretching vibration of
FIGURE 1 FT-IR spectra of
(a) MNP@SiO2, (b) MNP@SiO2@APTS,
(c) MNP@SiO2@APTS@DDMAT,
(d) MNP@PGMA, and (e) MNP@PGMA@DAP
FIGURE 2 TGA curves of (a) MNP@SiO2,
(b) MNP@SiO2@APTS,
(c) MNP@SiO2@APTS@DDMAT,
(d) MNP@PGMA, and (e) MNP@PGMA@DAP

6 of 15
POURJAVADI ET AL.
FIGURE 3 XRD patterns of
(a) MNP@SiO2, (b) MNP@PGMA, and
(c) MNP@PGMA@DAP@Au
FIGURE 4 (a) SEM image of MNP@PGMA@DAP and TEM images of (b) MNP@PGMA@DAP and (c) MNP@PGMA@DAP@Au

POURJAVADI ET AL.
7 of 15
FIGURE 5 VSM analyses of MNP and
MNP@PGMA@DAP
C–H. As shown in Figure 1c, the absorbance peaks at
1,627 and 2,924 cm–1 are attributed to the C=O of the
amide bond and aliphatic C–H bonds of the RAFT agent,
DAP with MNP@PGMA (Figure 1e), the new absorbance
peak at 1520 cm–1 is attributed to the N–H groups of
DAP.[47,65] Also, the peak at about 906 cm–1 disappeared,
indicating the ring-opening of oxirane rings by –NH2
groups of DAP. The results of the FT-IR analysis confirm
successful preparation of the solid support.
The TGA curves of the synthesized nanocomposites
are shown in Figure 2. The small weight loss in the range
of 100–200ꢀC in all curves is due to the removal of water
and other small molecules adsorbed on the surface of
MNP.[47] As shown in Figure 2b, the weight loss at
300–550ꢀC can be attributed to the thermal degradation of
the grafted aminopropyl groups in APTS. This weight loss
(about 5.19%) corresponds to about 0.895 mmol of APTS
respectively. Figure 1c indicates
a
successful
amidification reaction between C=O groups of the RAFT
agent (DDMAT) and amine groups (APTS) of the modi-
fied nanoparticles (MNP@SiO2@APTS). The absorbance
peak at 1735 cm–1 in the spectrum of MNP@PGMA
(Figure 1d) is related to ester carbonyl groups of PGMA
chains. Also, the characteristic peak at 906 cm–1 is attrib-
uted to the epoxy rings in grafted polymeric chains. The
results demonstrate that the polymer chains have been
successfully attached to the surface of MNP via the SI-
RAFT polymerization approach. After the reaction of
FIGURE 6 EDS analysis of
MNP@PGMA@DAP@Au

8 of 15
POURJAVADI ET AL.
TABLE 1 The effect of different parameters on the yield of the reduction of nitroarene[a]
Entry
1
Solvent
H2O
Amount of catalyst (mol%)
Amount of NaBH4 (mmol)
Time (min)
Yield (%)b
NR
35
-
1
1
2
3
5
1
3
5
2
2
2
2
2
3
3
10
2
3
3
3
3
60
45
30
20
15
10
7
2
Toluene
DMF
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.3
0.3
0.5
-
3
56
4
THF
44
5
H2O
63
6
H2O
57
7
H2O
72
8
H2O
6
87
9
H2O/EtOH
Methanol
DMSO
CH2Cl2
H2O
5
84
10
11
12
13
14
15
16
c17
18
19
20
21
8
42
10
60
7
30
NR
95
H2O
5
96
H2O
4
97
H2O
60
12
15
10
5
NR
68
H2O
0.5
0.5
0.5
0.5
0.5
DMF
65
THF
78
Methanol
H2O/EtOH
89
5
95
Bold indicates the optimal reaction conditions.
Note: NR, no reaction.
aReaction conditions: 4-nitrophenol (0.5 mmol, 0.069 g), catalyst MNP@PGMA@DAP@Au, and solvent (5 ml).
bIsolated yield,
cPGMA@DAP@Au.
(–NH2 groups) per gram of MNP@SiO2@APTS. Compared
with MNP@SiO2@APTS, the TGA curve of
MNP@SiO2@APTS@DDMAT (Figure 2c) shows decom-
position at the range of 200–700ꢀC (about 8.60%)
corresponding to APTS@DDMAT. The content of the
RAFT agent estimated from Figure 2c is about 0.247 mmol
per gram. In the TGA curve of MNP@PGMA (Figure 2d),
about 56 wt% of the sample is lost up to 800ꢀC, indicating
the PGMA content of MNP@PGMA is about 38.5 wt%. By
comparing the TGA curves of MNP@PGMA and
MNP@PGMA@DAP, it can be calculated that the DAP
content of the final nanocomposite is about 8 wt%.
can be seen that the diffraction peaks are a complete
match with the XRD diffraction peaks of a standard
Fe3O4 sample. Also, the broad peak in the XRD pat-
tern of samples at 2θ = 15–25ꢀ is related to the amor-
phous silica phase on the surface of MNP.[59,66] By
comparing the XRD patterns of MNP@SiO2,
MNP@SiO2@PGMA, and MNP@PGMA@DAP@Au, it
can be concluded that the various steps of the surface
modifications did not significantly change the micro-
structure of MNP@SiO2. Also, in the XRD pattern of
MNP@PGMA@DAP@Au (Figure 3c) there are addi-
tional peaks at 2θ = 38.25ꢀ, 44.32ꢀ, 64.65ꢀ, and 77.57ꢀ
(marked with asterisks), which are ascribed to the
(111), (200), (220), and (311) crystal planes of gold
Figure 3 displays the XRD patterns for MNP@SiO2,
MNP@SiO2@PGMA, and MNP@PGMA@DAP@Au. It

POURJAVADI ET AL.
9 of 15
TABLE 2 Catalytic reduction of nitroarene[a]
Entry
Substrate
Product
Time (min)
Yield (%)b
1
4-nitrophenol
4-aminophenol
4
3
97
93
91
90
97
89
92
96
93
92
88
93
96
89
92
2
1-chloro-4-nitrobenzene
1-chloro-3-nitrobenzene
4-chloro-2-nitroaniline
1-methoxy-4-nitrobenzene
2-nitroaniline
4-chloroaniline
3
3-chloroaniline
5
4
4-chlorobenzene-1,2-diamine
4-methoxyaniline
benzene-1,2-diamine
4-bromoaniline
8
5
3
6
6
7
1-bromo-4-nitrobenzene
4-nitroaniline
4
8
benzene-1,4-diamine
benzene-1,3-diamine
2-aminophenol
5
9
3-nitroaniline
6
10
11
12
13
14
15
2-nitrophenol
5
2-nitrobenzoic acid
3-nitrobenzaldehyde
1-methyl-3-nitrobenzene
4-nitrobenzoic acid
4-nitrobenzaldehyde
2-aminobenzoic acid
(3-aminophenyl)methanol
m-toluidine
10
3
4
4-aminobenzoic acid
(4-aminophenyl)methanol
8
4
aReaction conditions: nitroarenes (0.5 mmol), NaBH4 (3 mmol, 0.113 g), H2O (4 ml), MNP@PGMA@DAP@Au (0.5 mmol%).
bIsolated yield.
nanoparticles with a cubic structure. The XRD patterns
show that the Au nanoparticles were attached success-
fully to the surface of MNP@PGMA@DAP.[67,68]
TEM and SEM images of MNP@PGMA@DAP are
shown in Figure 4. The porous structure observed in
the SEM image of MNP@PGMA@DAP (Figure 4a) can
improve the metal adsorption by increasing the active
sites available for the catalyst. As seen in Figure 4b,
the gray shell encapsulated MNP (black core) is related
to the organic and silica phases. The TEM image also
shows good dispersion of nanoparticles onto the poly-
meric matrix. The TEM image of gold-loaded particles
is shown in Figure 4c. According to this figure, the
average diameter of the gold nanoparticles is about
5–7 nm.
Figure 5 shows the magnetization curves of MNP and
MNP@PGMA@DAP. It can be seen that MNP and
MNP@PGMA@DAP were both superparamagnetic with
saturation magnetization amounts of 55.06 and 38.6 emu
per gram. The lower saturation magnetization was
related to the surface modification of MNP with the dia-
magnetic layer (silica and polymer layers).[69,70]
The presence of Au, Fe, and Si in the catalyst was
confirmed by energy-dispersive X-ray spectroscopy (EDS)
as shown in Figure 6.
The loading amount of gold on MNP@ PGMA@DAP
supports was determined by atomic absorption spectros-
copy (AAS). The results show that the loading amount of
gold on the solid support is 0.52 mmol/g.
3.2 | Investigation of catalyst activity
(MNP@PGMA@DAP@au) for reduction of
nitroarenes
To
investigate
the
catalyst
activity
of
MNP@PGMA@DAP@Au in the reduction of nitro
arenas, 4-nitrophenol was selected as the model reaction.
The effect of reaction conditions on the yield of the reac-
tion was studied and the results are listed in Table 1. Ini-
tially, the reaction was performed without the catalyst,
however, no product was detected even after increasing
the amount of NaBH4 (entries 1 and 16). The reaction
was then performed in the presence of 0.1 mol% catalyst

10 of 15
POURJAVADI ET AL.
TABLE 3 Optimization of the Suzuki coupling reaction of 1-bromo-4-methoxybenzene and phenylboronic acid[a]
Entry
1
Amount of catalyst (mol%)
Solvent
H2O
Base
Time (hr)
Temp (ꢀC)
Yield (%)b
NR
40
–
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
NaOH
NaOAC
K2CO3
K2CO3
K2CO3
K2CO3
-
6
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
RT
40
80
100
2
0.2
0.2
0.2
0.2
0.3
0.4
0.4
0.4
0.4
0.5
0.4
0.4
0.5
0.5
0.5
0.5
0.5
0.5
H2O
3.25
5
3
Toluene
DMF
THF
27
4
8
NR
Trace
45
5
6
6
EtOH/H2O
H2O
3
7
2.45
3
87
8
H2O
83
9
H2O
3.5
4
72
10
11
12
13
c14
15
16
17
18
19
H2O
63
H2O
2.30
2.50
3.5
4.30
8
95
EtOH
EtOH/H2O
H2O
89
68
64
H2O
NR
NR
45
H2O
K2CO3
K2CO3
K2CO3
K2CO3
8
H2O
5
H2O
2
96
H2O
1.45
97
Bold indicates the optimal reaction conditions.
Note: NR, no reaction; RT, room temperature.
aReaction conditions: 1-bromo-4-methoxybenzene (1 mmol), phenylboronic acid (1.5 mmol), base (2 mmol), catalyst
(MNP@PGMA@DAP@Au), solvent (4 ml).
bIsolated yield.
cPGMA@DAP@Au.
and product was obtained with 56% yield. The result of
the prepared Au-loaded magnetic nanocomposite
behaves as a catalyst in this reaction. The influence of the
solvent was investigated by performing the reaction in
different solvents, including DMF, EtOH/H2O, methanol,
DMSO, CH2Cl2, and H2O. When CH2Cl2 was used as the
solvent, no product was detected (Table 1, entry 12).
However, by performing the reaction in toluene and
THF, products with 35% and 44% yields were obtained,
respectively (Table 1, entries 2 and 4). The yield of the
reaction increased to 56% by using DMF, a more polar
solvent. The best yield of the reaction (63%) was obtained
with water, indicating that polar solvents are more appro-
priate for this reaction. Water is an environmentally
friendly polar solvent that can be used for the reduction
of nitroarenes with 95% yield (Table 1, entry 13). The
effects of different solvents on the reduction of
nitroarenes with 3 mmol NaBH4 and 0.5 mol% catalyst
were explored. As shown in Table 1, H2O was the best
solvent for the reaction, with high yield of 97% (entry 15).
The effect of the amount of NaBH4 was also investi-
gated and the highest yield was obtained with 2 mmol of
NaBH4. The reaction was also carried out with different
amounts of catalyst and the best result was obtained with
0.5 mol% of the catalyst (Table 1, entry 15).
The reduction of different nitroarenes was explored
using the optimum reaction conditions obtained for the
model reaction. According to Table 2, the reduction of

POURJAVADI ET AL.
11 of 15
TABLE 4 Suzuki–Miyaura coupling reaction of various aryl halides[a]
Entry
Aryl halide
Product
Time (hr)
Yield (%)b
TON
190
186
186
182
180
172
178
180
TOF (h−1
)
1
2
3
4
5
6
7
8
Iodobenzene
1,10-biphenyl
1
95
93
93
91
90
86
89
90
190
143
56
Bromobenzene
1,10-biphenyl
1.30
3.30
2
Chlorobenzene
1,10-biphenyl
4-iodophenol
[1,10-biphenyl]-4-ol
4-methyl-1,10-biphenyl
4-nitro-1,10-biphenyl
4-methoxy-1,10-biphenyl
[1,10-biphenyl]-4-amine
91
1-bromo-4-methylbenzene
1-iodo-4-nitrobenzene
1-iodo-4-methoxybenzene
4-iodoaniline
2.20
3
81
57
2.30
2.30
77
78
Note: TOF, turnover frequency; TON, turnover number.
aReaction conditions: aryl halide (1 mmol), phenylboronic acid (1.5 mmol), K2CO3 (2 mmol), water (4 ml), MNP@PGMA@DAP@Au
(0.5 mol%).
bIsolated yield.
FIGURE 7 Recyclability of MNP@PGMA@DAP@Au for (a) Suzuki coupling and (b) reduction of nitroarenes
FIGURE 8 Leaching experiment. Suzuki–Miyaura reaction (a) in the presence of catalyst and (b) after hot filtration of the catalyst

12 of 15
POURJAVADI ET AL.
TABLE 5 The comparison of MNP@PGMA@DAP@Au with reported catalysts of Suzuki reaction
Entry
Catalyst
Solvent
DMF
–
Amount of catalyst
40 mg
Temp (ꢀC)
Time (hr)
Yield (%)
Ref.
1
2
3
4
5
6
7
Au-NPs supported on MgO
GO/Au-NPs
120
100
80
8
6
4
6
6
6
1
93
97
99
96
88
93
95
72
0.3 mol%
0.05 mol%
0.05 g
73
PATP-stabilized Au-NPs
Au-G nanocomposite
Au-Pd/MCM-41
H2O
H2O
H2O
H2O
H2O
30
70
74
0.130 g
80
75
76
Au-Nps@Hs-G-PMS hybrid
MNP@PGMA@DAP@Au
2 mol%
100
100
0.5 mol%
This work
Bold indicates the catalyst used in this work.
Note: Au-Nps@Hs-G-PMS, G, graphene; GO, Graphene Oxide; PATP, Poly (2-aminothiophenol).
nitroarenes containing various groups such as OH, CH3,
OCH3, and NH2 produced corresponding nitroamines in
excellent yields (Table 2, entries 7–9, 12, and 15).
Nitroarenes with halogen groups were also readily
reduced to the corresponding nitroamines (Table 2,
entries 2–5). The reduction of 2-nitrobenzoic acid and
4-nitrobenzoic acid was achieved in relatively lower
yields and in longer reaction times (Table 2, entries
11 and 14).
However, by using 0.2 mol % of the prepared
nanocomposite, product with 40% yield was obtained,
confirming the catalytic activity of the prepared mate-
rial (Table 3, entry 2). Toluene, DMF, THF, H2O,
EtOH/H2O, and EtOH were used as reaction solvents
and the best result was obtained when the reaction
was carried out in H2O. In toluene, the yield of the
product was 27%, but no significant amount of product
was obtained in DMF and THF (Table 3, entries 3–5).
The yield of the reaction increased to 87% and 95% by
increasing the catalyst amount to 0.4 and 0.5 mol%,
respectively (Table 3, entries 7 and 11). When ethanol
was used as the solvent, satisfactory results were
obtained (Table 3, entry 12). The reaction was also
performed the absence of the base, but no product was
detected even on increasing the amount of catalyst,
indicating that the base has an important effect on the
yield of the Suzuki reaction. Besides K2CO3, other
bases such as Cs2CO3, NaOH, and NaOAC were
employed in this reaction. However, K2CO3 showed
the best result with 95% yield (Table 3, entry 12). The
reaction was also carried out at different temperatures
(25, 40, 60, 80, and 100ꢀC) and the best result was
obtained at 60ꢀC (Table 3, entry 11).
3.3 | Investigation of catalyst activity
(MNP@PGMA@DAP@Au) in Suzuki
coupling reactions
After evaluation of the catalytic activity of
MNP@PGMA@DAP@Au in the reduction reaction, we
also tested the application of this catalyst in the Suzuki
coupling reaction. For this purpose, the reaction between
1-iodo-4-methoxybenzene and phenylboronic acid was
chosen as a model reaction and the effect of different
parameters on the yield of the reaction was studied. As
listed in Table 3, the results show that in the absence of
the catalyst, no product is obtained (Table 3, entry 1).
TABLE 6 The comparison between MNP@PGMA@DAP@Au catalyst and previously reported catalysts for reduction nitroarenes
Entry
Catalyst
Solvent
EtOH
EtOH/H2O
H2O
Amount of catalyst
1 mol%
Temp (ꢀC)
Time (min)
Yield(%)
Ref.
1
2
3
4
5
6
7
Au/MTA
RT
RT
RT
RT
RT
RT
RT
180
95
90
95
98
95
99
97
77
78
79
80
81
82
Starch-crt@Au
Au-GO
0.1 mol%
240
0.3 mol%
280
NAP-Mg–Au
Au/TiO2
H2O
75 mg
7
EtOH
H2O
0.1 mol%
20
Overnight
4
PEG/Au
0.3 mol%
MNP@PGMA@DAP@Au
H2O
0.5 mol%
This work
Bold indicates the catalyst used in this work.
Note: GO, Graphene Oxide; MTA, Mesoporous titania-supported gold nanoparticle assemblies; NAP, Nano Active plus; PEG, Polyethylene
glycol; Starch-crt@Au, Creatine-functionalized starch.

POURJAVADI ET AL.
13 of 15
Under the optimized conditions, the Suzuki reaction
was carried out on various aryl halides and the results
are summarized in Table 4. Aryl bromides and aryl
iodides containing electron-withdrawing or electron-
donating groups were successfully reacted and the
corresponding products were obtained in excellent yields.
In heterogeneous catalysis, the turnover frequency (TOF)
is determined as the average number of chemical reac-
tions happening on active sites per hour. The turnover
number (TON) is defined as the maximum number of
chemical conversions of aryl halides per second under
defined conditions.[35,71] The TON and TOF values for
the Suzuki coupling reaction with aryl bromides and aryl
iodides performed under optimum reaction conditions
are given in Table 4.
production of 4-methoxy-1,10-biphenyl was observed.
Moreover, the reaction mixture was analyzed using
induction coupled plasma spectroscopy (ICP-AES) and
no significant amount of gold species were detected. The
hot filtration test of catalyst confirms that
MNP@PGMA@DAP@Au is completely heterogeneous
and a slight decrease in the yield was attributed to the
loss of catalyst mass within the recovery and washing
processes.
3.5 | Comparison with other reported
catalyst systems for the Suzuki cross-
coupling reaction
The performance of MNP@PGMA@DAP@Au and the
previously reported catalyst is presented in Table 5. The
reaction between phenyl iodide and phenylboronic acid
was chosen as model reaction. The comparison between
MNP@PGMA@DAP@Au catalyst and previously
reported catalysts shows good catalytic activity towards
the Suzuki cross-coupling reaction and the synthesized
catalyst has advantages such as using water as solvent,
short time reaction, good separation, and reusability, also
the amount of applied catalyst was lower than other
catalysts.
3.4 | Recyclability of the catalyst
The
recyclability
of
the
prepared
catalyst
(MNP@PGMA@DAP@Au) was examined in the model
Suzuki reaction under the optimized conditions. At the
end of the reaction, the catalyst was separated, washed
with ethanol and water, and dried before the next runs.
The recyclability of the synthesized catalyst for the
Suzuki coupling reaction and reduction of nitroarenes is
shown in Figure 7. As displayed in Figure 7a, the pre-
pared catalyst was used for seven runs of the Suzuki cou-
pling reaction and a high yield of product was obtained
even after seven runs. The results indicate an increase in
the Suzuki coupling reaction time. This phenomenon can
be attributed to the mass loss of catalyst during catalyst
separation and recycling. The leaching of the catalyst was
also examined by atomic absorption spectroscopy and no
significant amount of leached gold was detected.
The reusability of the catalyst was also studied for the
reduction of 4-nitrophenol under the optimum reaction
conditions. The results show that the product was
obtained in high yield after 10 catalytic cycles
(Figure 7b).
The FT-IR spectra of fresh catalyst and used catalyst
after seven runs are shown in Supporting Information
Figure S4. By comparing the FT-IR spectra of the fresh
catalyst with that of the catalyst after seven runs, it can
be concluded that catalytic activity after seven runs did
not significantly change the FT-IR spectrum of fresh
catalyst.
3.6 | Comparison with other reported
catalyst systems for the reduction of
nitroarenes
As a comparison, Table 6 shows the activity of the cata-
lyst MNP@PGMA@DAP@Au with other reported cata-
lysts in the reduction of nitroarenes. The results indicate
that our catalyst system shows excellent catalytic activity
compared to other reported catalysts in the literature
(Table 6). Also after completion of the reaction, the cata-
lyst can be quickly separated and recovered by an exter-
nal magnet.
4 | CONCLUSION
We have demonstrated a strategy for the synthesis of a het-
erogeneous magnetic catalyst (MNP@PGMA@DAP@Au)
by RAFT polymerization. The heterogeneous catalyst was
successfully used for the reduction of nitroarenes and the
Suzuki reaction in water. A wide range of nitroarenes was
reduced under optimized reaction conditions. This
MNP@PGMA@DAP@Au catalyst has advantages such as
The leaching was examined for the coupling reaction
between 1-iodo-4-methoxybenzene and phenylboronic
acid as a model reaction under the optimized conditions
(Figure 8). After 75 min of reaction the catalyst was
completely separated then the reaction was allowed to
stir for another 75 min. The results show that no further

14 of 15
POURJAVADI ET AL.
[19] X. Duan, M. Xiao, S. Liang, Z. Zhang, Y. Zeng, J. Xi, S. Wang,
Carbon 2017, 119, 326. https://doi.org/10.1016/j.carbon.2017.
04.039
[20] A. Suzuki, J. Organomet. Chem. 1999, 576, 147. https://doi.org/
10.1016/s0022-328x(98)01055-9
high loading of gold, good to excellent yields, and easy
magnetic recovery. The catalyst has high efficiency after
seven runs without significant loss of catalytic activity in
the Suzuki reaction.
[21] S. Wei, Z. Ma, P. Wang, Z. Dong, J. Ma, J. Mol. Catal. A Chem.
2013, 370, 175. https://doi.org/10.1016/j.molcata.2013.01.012
[22] G. A. Grasa, M. S. Viciu, J. Huang, C. Zhang, M. L. Trudell,
S. P. Nolan, Organometallics 2002, 21, 2866. https://doi.org/10.
1021/om020178p
ORCID
Ali Pourjavadi https://orcid.org/0000-0003-4180-4358
REFERENCES
[23] A. Balanta, C. Godard, C. Claver, Chem. Soc. Rev. 2011, 40,
4973. https://doi.org/10.1039/c1cs15195a
[1] P. Selvam, S. U. Sonavane, S. K. Mohapatra, R. V. Jayaram,
Tetrahedron Lett. 2004, 45, 3071. https://doi.org/10.1016/j.
tetlet.2004.02.098
[24] M. E. Martínez-Klimov, P. Hernández-Hipólito, M. Martínez-
García, T. E. Klimova, Catal. Today 2018, 305, 58. https://doi.
org/10.1016/j.cattod.2017.10.015
ꢀ
ꢀ
ꢀ
[2] I. Pogorelic, M. Filipan-Litvic, S. Merkaš, G. Ljubic,
ꢀ
I. Cepanec, M. Litvic, J. Mol. Catal. A Chem. 2007, 274, 202.
https://doi.org/10.1016/j.molcata.2007.05.020
[3] A. Corma, P. Concepción, P. Serna, Angew. Chem. Int. Ed.
2007, 46, 7133. https://doi.org/10.1002/anie.200790188
[4] K. Manjunatha, T. S. Koley, V. Kandathil, R. B. Dateer,
G. Balakrishna, B. S. Sasidhar, S. A. Patil, S. A. Patil, Appl.
Organomet. Chem. 2018, 32, e4266. https://doi.org/10.1002/
aoc.4266
[5] F. Cárdenas-Lizana, S. Gómez-Quero, N. Perret, M. A. Keane,
Catal. Sci. Technol. 2011, 1, 652. https://doi.org/10.1039/
c1cy00051a
[6] T. Aditya, A. Pal, T. Pal, Chem. Commun. 2015, 51, 9410.
https://doi.org/10.1039/c5cc01131k
[7] A. Pourjavadi, N. Keshavarzi, F. M. Moghaddam,
S. H. Hosseini, Appl. Organomet. Chem. 2018, 32. https://doi.
org/10.1002/aoc.4107
[25] Y. Liu, Y. Wu, C. Xi, Appl. Organomet. Chem. 2009, 23, 329.
https://doi.org/10.1002/aoc.1516
[26] L. Liu, K. Zhao, W. Li, M. Liu, Y. Chen, Y. Dong, Appl.
Organomet. Chem. 2019, 33, e4831. https://doi.org/10.1002/
aoc.4831
[27] D. Zim, V. R. Lando, J. Dupont, A. L. Monteiro, Org. Lett.
2001, 3, 3049. https://doi.org/10.1021/ol016526l
[28] M. B. Thathagar, J. Beckers, G. Rothenberg, J. Am. Chem. Soc.
2002, 124, 11858. https://doi.org/10.1021/ja027716+
[29] J. Han, Y. Liu, R. Guo, J. Am. Chem. Soc. 2009, 131, 2060.
https://doi.org/10.1021/ja808935n
[30] M. Nasrollahzadeh, F. Babaei, P. Fakhri, B. Jaleh, RSC Adv.
2015, 5, 10782. https://doi.org/10.1039/c4ra12552e
[31] G. Li, R. Jin, Nanotechnol. Rev. 2013, 2, 529. https://doi.org/10.
1515/ntrev-2013-0020
[8] S. Nishimura, Handbook of Heterogeneous Catalytic Hydroge-
nation for Organic Synthesis, Wiley-Interscience Publication
John-Wiley, New York 2001.
[9] M. Pietrowski, Curr. Org. Synth. 2012, 9, 470. https://doi.org/
10.2174/157017912802651456
[10] M. Kumar, U. Sharma, S. Sharma, V. Kumar, B. Singh,
N. Kumar, RSC Adv. 2013, 3, 4894. https://doi.org/10.1039/
c3ra40771c
[11] R. V. Jagadeesh, A.-E. Surkus, H. Junge, M.-M. Pohl,
J. Radnik, J. Rabeah, H. Huan, V. Schunemann, A. Bruckner,
M. Beller, Science 2013, 342, 1073. https://doi.org/10.1126/
science.1242005
[32] D. J. Cole-Hamilton, Science 2003, 299, 1702. https://doi.org/
10.1126/science.1081881
[33] S. Minakata, M. Komatsu, Chem. Rev. 2009, 109, 711. https://
doi.org/10.1021/cr8003955
[34] B. Maleki, O. Reiser, E. Esmaeilnezhad, H. J. Choi, Polyhedron
2019, 162, 129. https://doi.org/10.1016/j.poly.2019.01.055
[35] D. Wang, J. Liu, J. Xi, J. Jiang, Z. Bai, Appl. Surf. Sci. 2019,
489, 477. https://doi.org/10.1016/j.apsusc.2019.06.039
[36] L. Tang, X. Guo, Y. Yang, Z. Zha, Z. Wang, Chem. Commun.
2014, 50, 6145. https://doi.org/10.1039/c4cc01822b
[37] S. S. Liu, X. Liu, L. Yu, Y. M. Liu, H. Y. He, Y. Cao, Green
Chem. 2014, 16, 4162.
[12] J. Xi, J. Xiao, F. Xiao, Y. Jin, Y. Dong, F. Jing, S. Wang, Sci.
Rep. 2016, 6. https://doi.org/10.1038/srep21904
[13] R. J. Rahaim, R. E. Maleczka, Org. Lett. 2005, 7, 5087. https://
doi.org/10.1021/ol052120n
[14] J. Liu, J. Hao, C. Hu, B. He, J. Xi, J. Xiao, S. Wang, Z. Bai,
J. Phys. Chem. 2018, 122, 2696. https://doi.org/10.1021/acs.
jpcc.7b10237
[38] M. Boominathan, N. Pugazhenthiran, M. Nagaraj,
S. Muthusubramanian, S. Murugesan, N. Bhuvanesh, ACS
Sustainable Chem. Eng. 2013, 1, 1405.
[39] H. J. Cho, S. Jung, S. Kong, S. J. Park, S. M. Lee, Y. S. Lee,
Adv. Synth. Catal. 2014, 356, 1056.
[40] F. Shi, Q. Zhang, Y. Ma, Y. He, Y. Deng, ChemInform 2005,
36, 4182.
[15] X. Duan, J. Liu, J. Hao, L. Wu, B. He, Y. Qiu, J. Zhang, Z. He,
J. Xi, S. Wang, Carbon 2018, 130, 806. https://doi.org/10.1016/
j.carbon.2018.01.038
[16] M. Wen, S. Takakura, K. Fuku, K. Mori, H. Yamashita, Catal.
Today 2015, 242, 381. https://doi.org/10.1016/j.cattod.2014.
05.019
[17] L. Chen, Z. Gao, Y. Li, Catal. Today 2015, 245, 122. https://
doi.org/10.1016/j.cattod.2014.03.074
[18] S. Jadhav, A. Kumbhar, R. Salunkhe, Appl. Organomet. Chem.
2015, 29, 339. https://doi.org/10.1002/aoc.3290
[41] B. Maleki, E. R. Seresht, Z. Ebrahimi, Org. Prep. Proced. Int.
2015, 47, 149.
[42] B. Karimi, F. Kabiri Esfahani, Chem. Commun. 2011, 47,
10452.
[43] B. Maleki, H. Eshghi, A. Khojastehnezhad, R. Tayebee,
S. S. Ashrafi, G. E. Kahoo, F. Moeinpour, RSC Adv. 2015, 5,
64850.
[44] J. Lin, W. Zhou, A. Kumbhar, J. Wiemann, J. Fang,
E. E. Carpenter, C. J. O'Connor, J. Solid State Chem. 2001,
159, 26.

POURJAVADI ET AL.
15 of 15
[45] X. C. Shen, X. Z. Fang, Y. H. Zhou, H. Liang, Chem. Lett. 2004,
33, 1468.
[70] J. Qu, G. Liu, Y. Wang, R. Hong, Adv. Powder Technol. 2010,
21, 461.
[46] G. Mohammadi Ziarani, Z. Kazemi Asl, P. Gholamzadeh,
A. Badiei, M. Afshar, Appl. Organomet. Chem. 2017, 31, 1.
[47] A. Pourjavadi, M. Kohestanian, M. Yaghoubi, New J. Chem.
2019, 43, 18647.
[71] J. Xi, H. Sun, D. Wang, Z. Zhang, X. Duan, J. Xiao, F. Xiao,
L. Liu, S. Wang, Appl. Catal. B Environ. 2018, 225, 291.
[72] H. Liu, J. Bai, C. Li, W. Xu, W. Sun, T. Xu, Y. Huang, H. Li,
RSC Adv. 2014, 4, 3195.
[48] B. Zhang, Y. Chen, L. Xu, L. Zeng, Y. He, E.-T. Kang,
J. Zhang, J. Polym. Sci. Part a Polym. Chem. 2011, 49, 2043.
[49] Y. S. Ye, Y. N. Chen, J. S. Wang, J. Rick, Y. J. Huang,
F. C. Chang, B. J. Hwang, Chem. Mater. 2012, 24, 2987.
[50] R. Gu, W. Z. Xu, P. A. Charpentier, Polymer 2014, 55, 5322.
[51] B. Hojjati, R. Sui, P. A. Charpentier, Polymer 2007, 48, 5850.
[52] B. Hojjati, P. A. Charpentier, Polymer 2010, 51, 5345.
[53] A. Pourjavadi, M. Kohestanian, M. Shirzad, Colloids Surfaces B
Biointerfaces 2019, 174, 153.
[73] M.
Nasrollahzadeh,
M.
Atarod,
B.
Jaleh,
M. Gandomirouzbahani, Ceram. Int. 2016, 42, 8587.
[74] P. Mondal, N. Salam, A. Mondal, K. Ghosh, K. Tuhina,
S. M. Islam, J. Colloid Interface Sci. 2015, 459, 97.
[75] M. G. Speziali, A. G. M. Da Silva, D. M. V. De Miranda,
A. L. Monteiro, P. A. Robles-Dutenhefner, Appl. Catal. A Gen.
2013, 462, 39.
[76] S. K. Movahed, M. Shariatipour, M. Dabiri, RSC Adv. 2015, 5,
33423.
[54] Z. P. Xiao, K. M. Yang, H. Liang, J. Lu, J. Polym. Sci. Part A
Polym. Chem. 2010, 48, 542.
[55] C. Gonzato, M. Courty, P. Pasetto, K. Haupt, Adv. Funct.
Mater. 2011, 21, 3947.
[77] S. Fountoulaki, V. Daikopoulou, P. L. Gkizis, I. Tamiolakis,
G. S. Armatas, I. N. Lykakis, ACS Catal. 2014, 4, 3504.
[78] M. Gholinejad, N. Dasvarz, M. Shojafar, J. M. Sansano,
Inorganica Chim. Acta 2019, 495, 118965.
[56] Y. Zhao, S. Perrier, Radic. Polym. Kinet. Mech. 2007, 94.
[57] A. Pourjavadi, S. Rahemipoor, M. Kohestanian, Compos. Sci.
Technol. 2020, 188, 107951.
[58] D. Wang, H. Duan, J. Lü, C. Lü, J. Mater. Chem. A 2017, 5,
5088.
[79] P. Fakhri, M. Nasrollahzadeh, B. Jaleh, RSC Adv. 2014, 4,
48691.
[80] K. Layek, M. L. Kantam, M. Shirai, D. Nishio-Hamane,
T. Sasaki, H. Maheswaran, Green Chem. 2012, 14, 3164.
[81] E. Vasilikogiannaki, C. Gryparis, V. Kotzabasaki,
I. N. Lykakis, M. Stratakis, Adv. Synth. Catal. 2013, 355, 907.
[82] Y. Uozumi, S. Pan, Synfacts 2016, 12(01), 0104.
[59] A. Pourjavadi, M. Kohestanian, C. Streb, Mater. Sci. Eng. C
2020, 108, 110418.
[60] C. Barner-Kowollik, Handbook of RAFT Polymerization, John
Wiley & Sons, Weinheim 2008.
[61] A. Chen, J. Qi, Q. Zhao, Y. Li, G. Zhang, F. Zhang, X. Fan,
RSC Adv. 2013, 3, 8973.
[62] S. Ghasemi, S. Karim, Mater. Chem. Phys. 2018, 205, 347.
[63] M. Kohestanian, H. Bouhendi, M. Ghiass, J. Polym. Res. 2017,
24, 194.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
[64] M. Kohestanian, H. Bouhendi, Colloid Polym. Sci. 2015, 293,
1983.
[65] J. Tan, D. Liu, C. Huang, X. Li, J. He, Q. Xu, L. Zhang,
Macromol. Rapid Commun. 2017, 38, 1.
[66] G. Tan, W. Li, J. Cheng, Z. Wang, S. Wei, Y. Jin, C. Guo,
F. Qu, Photochem. Photobiol. Sci. 2016, 15, 1567.
[67] Z. Wang, L. Wu, F. Wang, Z. Jiang, B. Shen, J. Mater. Chem. A
2013, 1, 9746.
[68] X. Zhang, Y. Zhu, X. Yang, Y. Zhou, Y. Yao, C. Li, Nanoscale
2014, 6, 5971.
How to cite this article: Pourjavadi A,
Kohestanian M, Keshavarzi N. Immobilization of
Au nanoparticles on poly(glycidyl methacrylate)-
functionalized magnetic nanoparticles for
enhanced catalytic application in the reduction of
nitroarenes and Suzuki reaction. Appl Organomet
Chem. 2020;e5828. https://doi.org/10.1002/aoc.
5828
[69] Q. Zhang, J. Kang, B. Yang, L. Zhao, Z. Hou, B. Tang, Chinese
J. Catal. 2016, 37, 389.