Mizoroki–Heck and Suzuki–Miyaura reactions mediated by poly(2-acrylamido-2-methyl-1-propanesulfonic acid)-stabilized magnetically separable palladium catalyst

Article abstract of DOI:10.1002/aoc.4346

The purpose of this work was to synthesize and characterize a new magnetic polymer nanosphere-supported palladium(II) acetate catalyst for reactions requiring harsh conditions. In this regard, an air-stable, moisture-stable and highly efficient heterogenized palladium was synthesized by the coordination of palladium(II) acetate with poly(2-acrylamido-2-methyl-1-propanesulfonic acid)-grafted modified magnetic nanoparticles with a core–shell structure. The structure of the newly developed catalyst was characterized using various techniques. The catalytic activity of the resultant nano-organometallic catalyst was evaluated in Mizoroki–Heck and Suzuki–Miyaura reactions to afford the corresponding coupling products in good to excellent yields. High selectivity as well as outstanding turnover number (14 143, 4900) and turnover frequency (28 296, 7424) values were recorded for the catalyst in Suzuki–Miyaura and Mizoroki–Heck reactions, respectively. Magnetic separation and recycling of the catalyst for at least six runs became possible without any significant loss of efficiency or any detectable palladium leaching.

Full text of DOI:10.1002/aoc.4346

Received: 27 December 2017
DOI: 10.1002/aoc.4346
Revised: 5 February 2018
Accepted: 11 February 2018
F U L L P A P E R
Mizoroki–Heck and Suzuki–Miyaura reactions mediated by
poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐
stabilized magnetically separable palladium catalyst
Maryam Arghan
| Nadiya Koukabi
| Eskandar Kolvari
Department of Chemistry, Semnan
University, PO Box 35195‐363, Semnan,
Iran
The purpose of this work was to synthesize and characterize a new magnetic
polymer nanosphere‐supported palladium(II) acetate catalyst for reactions
requiring harsh conditions. In this regard, an air‐stable, moisture‐stable and
highly efficient heterogenized palladium was synthesized by the coordination
of palladium(II) acetate with poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic
acid)‐grafted modified magnetic nanoparticles with a core–shell structure.
The structure of the newly developed catalyst was characterized using various
techniques. The catalytic activity of the resultant nano‐organometallic catalyst
was evaluated in Mizoroki–Heck and Suzuki–Miyaura reactions to afford the
corresponding coupling products in good to excellent yields. High selectivity
as well as outstanding turnover number (14 143, 4900) and turnover frequency
Correspondence
Nadiya Koukabi, Department of
Chemistry, Semnan University, PO Box
35195‐363, Semnan, Iran.
Email: n.koukabi@semnan.ac.ir
Funding information
Semnan University Research Council
(28 296, 7424) values were recorded for the catalyst in Suzuki–Miyaura and
Mizoroki–Heck reactions, respectively. Magnetic separation and recycling of
the catalyst for at least six runs became possible without any significant loss
of efficiency or any detectable palladium leaching.
KEYWORDS
heterogeneous palladium catalyst, magnetic polymer‐supported palladium, Mizoroki–Heck coupling
reaction, Suzuki–Miyaura coupling reaction
1
| INTRODUCTION
as one of the most powerful tools for carbon–carbon
[
5–8]
bond formation in organic synthesis.
Principally,
One of the foundational reactions in organic synthesis is
the formation of carbon–carbon bonds because of its
many applications in the synthesis of numerous drugs,
natural products and high‐performance modern mate-
rials. The Mizoroki–Heck and Suzuki–Miyaura coupling
reactions are particularly versatile methods for forming
the palladium‐catalysed Mizoroki–Heck and Suzuki–
Miyaura coupling reactions are carried out homoge-
[
9,10]
[11,12]
neously in water,
liquids.
organic media
or ionic
[
13,14]
Although catalytic activities of homoge-
neous catalysts are higher than those of their heteroge-
neous counterparts, they suffer from important
drawbacks such as laborious recovery and recycling of
the catalyst, purification of final products and deactiva-
[1]
carbon–carbon bonds. A significant number of reviews
have focused on these reactions, due to their high impact
and experimental importance in the generation of fine
[
15]
tion of the catalyst.
In addition, because of the high
[2–4]
chemicals and pharmaceuticals.
In this regard, many
toxicity and cost of palladium, its removal from organic
[16]
effective catalytic systems have been designed and devel-
oped for this reaction. Palladium catalysis has emerged
products at the end of a reaction is very important.
So, heterogeneous catalytic systems are drawing
Appl Organometal Chem. 2018;e4346.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
1 of 16
https://doi.org/10.1002/aoc.4346

2
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ARGHAN ET AL.
[
28,29]
considerable attention due to the desirability of recovery
and reuse of valuable palladium catalysts.
particular importance in many fields of application.
Polymers tethered to inorganic surfaces like SiO ,
[30]
2
[
31,32]
[33]
[34]
[35]
The immobilization of palladium on various solid sup-
ports has led to the development of several types of het-
Fe O ,
ZnO,
Au
or alumina
have attracted
3
4
extensive research interest due to the ability to modify
the surface characteristics and have applications in basic
and applied interfacial studies. One of the most promising
support matrices, for incorporation of polymer species, is
superparamagnetic iron oxide nanoparticles with high
surface area, which are easily obtained from commer-
cially available materials such as FeCl ⋅6H O and
[17,18]
erogeneous palladium catalysts.
The support is one
of the most important and key factors in heterogeneous
catalyst systems, because it plays a crucial role in longev-
ity, conversion yield and thermal and mechanical stability
[19,20]
of the catalyst.
These parameters principally deter-
mine whether a catalyst is practicable for industrial pro-
cesses. Most supports are materials with properties like
reusability, ready availability, eco‐friendliness and low
3
2
[
36]
FeCl ⋅4H O in water.
The facile recovery of a catalyst
2
2
that can be manipulated using magnetic fields is the
prime advantage of using magnetic nanoparticles (MNPs)
as supports, for which the catalyst loss problem during
the filtration at the end of the reaction is solved. The con-
venient functionality of MNPs with various coupling
agents is another advantage, because they prevent the cat-
alyst from leaching during the reaction due to the strong
chemical interaction between the organocatalyst and the
metallic support. So, polymer–MNP composites have
emerged as promising and robust materials because they
combine the advantages of MNPs (e.g. thermal stability,
large surface area and magnetic properties) and organic
polymers (e.g. pH stability and chemical functionality).
[21,22]
cost.
However, there are disadvantages from which
these supported catalysts suffer, such as leaching of palla-
dium from catalyst to reaction mixture and easy agglom-
eration. So, the development of new catalysts that are
simultaneously active and stable, as well as easy to sepa-
rate and reuse is of much importance as it will surely
facilitate actual practical applications in carbon–carbon
coupling reactions. The supported catalysts are based on
[
23,24]
[25,26]
inorganic,
tures.
(bio)organic
and hybrid struc-
[
27]
The chemical and physical properties of hybrid
organic–inorganic materials are not only the sum of the
single contributions of both phases, but also the result
of synergy of both parts, depending on the size distribu-
tion and spatial arrangement of their constituents, so
hybrid materials play a vital role in the development of
advanced functional materials.
[37]
There are three methods of synthesis, ‘grafting to’,
[
38]
[39]
‘grafting from’
and ‘grafting through’,
that are used
to construct a graft polymer. Figure 1 illustrates various
strategies for surface grafting with a polymer.
In this regard, polymer grafting on inorganic, metal or
carbon‐based surfaces, known as polymer brushes, is of
Considerable effort has been made over time to
develop more palladium–polymer hybrid catalysts.
[40–42]
FIGURE 1 The most common
techniques of polymer grafting

ARGHAN ET AL.
3 of 16
Despite the considerable success achieved in the field of
polymeric stabilizers, it is a challenging task to develop
hydrophilic functional groups attached to a polymeric
backbone, such as ─COOH, ─SO H, ─CONH , ─NH
2
palladium in the catalyst was measured using inductively
coupled plasma optical emission spectrometry (ICP‐OES)
with a Varian VISTA‐PRO. NMR spectra were measured
in pure dimethylsulfoxide (DMSO) with a Bruker
3
2
1
13
and ─OH, for the incorporation of metals, especially in
the case of Mizoroki–Heck and Suzuki–Miyaura coupling
reactions. In this paper, we introduce the design of a
highly dispersed catalytic system in green environment
which can be separated from a reaction mixture and
recycled easily several times without considerable loss of
its catalytic activity. In this line, we report a novel cata-
lytic system, denoted as MNP@PAMPS‐Pd(II), involving
Pd(II) supported on poly(2‐acrylamido‐2‐methyl‐1‐
propanesulfonic acid) (PAMPS)‐grafted modified MNPs
with a core–shell structure. To the best of our knowledge,
there are no literature reports on the synthesis of PAMPS‐
grafted modified MNPs with a core–shell structure
through a ‘grafting from’ approach. Finally, we report a
study of the efficiency of our new and reusable catalyst
in the Mizoroki–Heck and Suzuki–Miyaura cross‐cou-
pling reactions. High turnover number (TON) and turn-
over frequency (TOF) values were exciting results for
Advance 400 MHz instrument ( H NMR: 400 MHz;
C
NMR: 125 MHz) with tetramethylsilane as the internal
reference. Detection of products was performed with a
gas chromatograph (GC‐17A, Shimadzu, Japan) equipped
with a splitless/split injector and a flame ionization detec-
tor. Helium (purity 99.999%) was used as the carrier gas at
−
1
a constant flow rate of 4 ml min . The temperatures of
injector and detector were set at 275 and 320 °C, respec-
tively. The injection port was operated in splitless mode
and with sampling time of 1 min. For flame ionization
detection, hydrogen gas was generated with a hydrogen
generator (OPGU‐2200S, Shimadzu, Japan). A 30 m BP‐
10 SGE fused‐silica capillary column (0.32 mm i.d. and
0.25 μm film thickness) was applied for separation of
products. Oven temperature programme was: started
from 60 °C, held for 3 min, increased to 190 °C at
−
1
20 °C min , held for 0 min, increased to 240 °C at
−
1
10 °C min and then held for 3 min. A 10.0 μl ITO (Fuji,
Japan) micro‐syringe was applied for the collection of
sedimented organic solvent and injection into the
chromatograph.
3
the catalyst in both reactions. Catalysts with TON > 10
[43]
are deemed as HTC supports.
2
2
| EXPERIMENTAL
.1 | General Remarks
2
2
.2 | Catalyst Preparation
The chemicals, reagents and solvents were employed
without further purification and purchased from Merck
and Sigma‐Aldrich. Fourier transform infrared (FT‐IR)
spectra were recorded with a Shimadzu 8400 s spectrom-
eter using KBr pressed powder discs. Magnetic measure-
ments were carried out using vibrating sample
magnetometry (VSM; Lakeshore 7407) at room tempera-
ture. The crystalline structures of the samples were evalu-
ated by X‐ray diffraction (XRD) analysis at room
temperature on with a Siemens D5000 (Siemens AG,
Munich, Germany) using Cu Ka radiation of wavelength
of 1.54 Å. Field‐emission scanning electron microscopy
.2.1 | Synthesis of modified magnetic
nanoparticles (MNP@IA)
In order to increase the stability, impede the agglomera-
tion of MNPs and provide reactive C═C bonds, the sur-
face of Fe O nanoparticles was modified with itaconic
3 4
acid (IA). For this purpose, magnetite nanoparticles were
prepared using a modified procedure based on a previ-
ously reported method. In a typical synthesis, 2.5 mmol
of FeCl ⋅4H O and 5.0 mmol of FeCl ⋅6H O were dis-
solved in 10 ml of ultrapure water. This solution was
added dropwise into an aqueous solution of ammonium
hydroxide (2 wt%) at 90 °C under vigorous magnetic stir-
ring. After 30 min, the black material formed was col-
lected with a magnet to remove the supernatant. All
steps were performed under nitrogen atmosphere. The
modification of the iron oxide particles was then achieved
by adding a mixture of 0.7 mmol of IA dissolved in 5.0 ml
of an aqueous solution of ammonia (2 wt%). After 1 h of
stirring at 50 °C, the modified MNP@IA was obtained,
which was magnetically separated, washed three times
with ethanol and deionized water to remove any excess
reagent and salts, and then dried in a vacuum oven
overnight.
[
44]
2
2
3
2
(Fe‐SEM) and energy‐dispersive X‐ray (EDX) analysis
were done to obtain information about the particle size,
morphology and elemental mapping of the catalyst using
a TESCAN MIRA II digital scanning microscope. Trans-
mission electron microscopy (TEM) images were obtained
with a CM120 microscope (Philips). The purity of prod-
ucts was determined using TLC on commercial plates
coated with silica gel 60 F254 using n‐hexane–ethyl ace-
tate mixture as the mobile phase. Thermogravimetric
analysis (TGA) was done using a DuPont 2000 thermal
analysis apparatus heated from 25 to 1000 °C at a ramp
−
1
of 5 °C min under air atmosphere. The amount of

4
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ARGHAN ET AL.
2
.2.2 | Polymerization and synthesis of
2.3.2 | MNP@PAMPS‐Pd(II)‐catalysed
Mizoroki–Heck reaction: general procedure
MNP@PAMPS nanocomposite
For the polymerization of the desired monomers on the
surface of the modified Fe O nanoparticles, in a typical
A mixture of aryl halide (1.0 mmol), olefin (1.5 mmol),
K CO3
(2.0
mmol)
and
MNP@PAMPS‐Pd(II)
3
4
2
experiment,
2‐acrylamido‐2‐methyl‐1‐propanesulfonic
(0.02 mol%) as catalyst in 3 ml of dimethylformamide
(DMF) was added to a round‐bottom flask with a mag-
netic stirrer. The mixture was stirred at 100 °C for an
appropriate time. After the completion of the reaction as
monitored by TLC, the magnetic catalyst was separated
using an external magnet and the reaction mixture was
cooled to room temperature. The reaction mixture was
extracted with ethyl acetate. The organic layer was dried
acid (AMPS; 1.0 g) was added to a flask containing 1 g
of modified Fe O nanoparticles suspended in 12 ml of
deionized water. Then, the mixture was purged under
nitrogen gas for 15 min to remove dissolved oxygen. Sub-
sequently, 0.053 g of ammonium persulfate as an initiator
was added to the reaction mixture, and kept at 60 °C for
3
4
2
4 h to complete the polymerization. Finally, the obtained
PAMPS‐coated MNPs were separated from the suspen-
sion using an external magnet and washed with ethanol
and water (three times) to eliminate excess reactants
and then dried in a vacuum oven for 24 h at 50 °C to
afford the MNP@PAMPS nanocomposite.
over anhydrous MgSO . Some products were character-
4
1
13
ized using H‐NMR and C‐NMR spectroscopic tech-
niques and the results are presented in the supporting
information.
2.3.3 | Reusability of catalyst
2
.2.3 | Synthesis of Pd(II) supported on
PAMPS‐grafted modified MNPs
MNP@PAMPS‐Pd(II))
Reusability of the nanocatalyst was investigated using the
reaction of iodobenzene with phenylboronic acid under
already determined optimized conditions. At the end of
the reaction, the separated catalyst was washed with
water and ethanol to remove salt and adsorbed organic
substrates, respectively, and reused in subsequent runs
with new portions of reagents without any pre‐treatment.
(
MNP@PAMPS (0.5 g), Pd(OAc) (0.1 g) and deionized
2
water (50 ml) were placed into a round‐bottom flask
and sonicated for 45 min. Then, the reaction was left to
stir for 12 h at room temperature. The final palladium
complex (MNP@PAMPS‐Pd(II)) was magnetically sepa-
rated and washed several times with distilled water, etha-
nol and acetonitrile for any excess reagent to be removed
and finally dried in a vacuum oven at 60 °C for 24 h.
3
3
| RESULTS AND DISCUSSION
.1 | Synthesis and Characterization of
MNP@PAMPS‐Pd(II)
2
.3 | Investigations of Catalytic Activity
.3.1 | MNP@PAMPS‐Pd(II)‐catalysed
As already mentioned, several types of heterogeneous pal-
ladium catalysts have been developed by immobilizing
palladium on various solid supports. So, the aim of the
study reported here was to develop a new system of palla-
dium immobilized onto a suitable support to overcome
most of the problems associated with the use of homoge-
neous palladium catalysts. In this line, we decided to syn-
thesize a novel polymer‐stabilized magnetically separable
palladium catalyst. Design of the heterogeneous Pd(II)
catalyst was carried out according to a concise route, as
outlined in Scheme 1. Initially, before coating of the poly-
mer onto the Fe O surface, the surface of the MNPs was
2
Suzuki–Miyaura reaction: general
procedure
A mixture of phenylboronic acid (1.2 mmol), aryl halide
(1.0 mmol), K CO (3.0 mmol) and MNP@PAMPS‐Pd(II)
2
3
(0.007 mol%) as catalyst in 5 ml of ethanol–water (1: 1)
was added to a round‐bottom flask with a magnetic stirrer
and placed in an oil bath to keep the temperature at
reflux temperature (80 °C) for the required period of time
(reaction was monitored by TLC). After the completion of
3
4
the reaction, the catalyst was separated using an external
magnet. Then, after the reaction mixture was cooled to
room temperature, it was extracted with ethyl acetate.
After the extraction of the aqueous layer, the organic
layer was washed with water and dried over anhydrous
modified with IA to give reactive C═C bonds on the sur-
face of Fe O . The presence of vinyl groups on the surface
3
4
of Fe O gives two important results. First, it makes poly-
3
4
merization easier on the surface of MNPs. The copolymer
is grafted onto the surface of MNP through covalent
[
45]
MgSO . Some products were characterized using GC‐FID
bonds.
Second, without IA modification, only a minor
4
1
13
and H‐NMR and C‐NMR spectroscopic techniques and
part of the MNPs can be coated with a complete layer of
[
45]
the results are presented in the supporting information.
polymer chains.
Subsequently, the MNP@PAMPS

ARGHAN ET AL.
5 of 16
SCHEME 1 Procedure for preparation
of MNP@PAMPS‐Pd(II)
nanocomposite was obtained by the polymerization of
3.1.1 | FT‐IR spectra
AMPS as a monomer in the presence of modified Fe O4
3
The FT‐IR spectra of Fe O , AMPS, MNP@PAMPS and
3
4
using ammonium persulfate as an initiator for radical
polymerization to produce the desired polymer. Finally,
the resulting MNP@PAMPS was reacted with palladium
acetate in water to form the MNP@PAMPS‐Pd(II) cata-
MNP@PAMPS‐Pd(II) are depicted in Figure 2 to confirm
the modification of the magnetite surface with the
organic polymer shell. All magnetic samples show two
bands at around 557 and 570 cm , corresponding to
Fe─O stretching vibration (Figure 2a,c,d). After the
−
1
lyst. As one can see, PAMPS as a ligand carrying SO H
3
and CONH functional groups could immobilize palla-
2
[46]
dium, through oxygen and nitrogen atoms.
Therefore,
there is no need for an additional ligand. Furthermore,
PAMPS has hydrophilic character which can be consid-
ered as another important reason for choosing this poly-
mer as polymeric segment. The amount of palladium
−
1
loaded was found to be 0.73 mmol g (determined by
ICP‐OES analysis). As can be seen, the palladium content
of the catalyst is very significant compared to that of some
other solid‐supported palladium complexes, which can be
due to multilayer and polymeric nature of the coated
material on the surface of the MNPs that allows many
functional groups to immobilize palladium. To prove the
structure of catalyst, elucidate any errors during the prep-
aration procedure and investigate the stability of the cata-
lyst before and after the catalytic reaction,
a
comprehensive characterization was achieved using FT‐
IR spectroscopy, XRD, TGA, TEM, VSM, FE‐SEM, ICP‐
OES and EDX analysis.
FIGURE 2 FT‐IR spectra of (a) Fe
(c) MNP@PAMPS and (d) MNP@PAMPS‐Pd(II)
3 4
O nanoparticles, (b) AMPS,

6
of 16
ARGHAN ET AL.
polymerization process, characteristic absorption peaks at
−
1
1
041 and 1120 cm are attributed to the stretching vibra-
tions of S═O of sulfonic acid, associated with PAMPS
−
1
(
Figure 2b,c). The bands at 1400 and 1635 cm result
from the stretching of C─N and stretching of amidic
C═O bonds, respectively (Figure 2b,c). In addition, the
−
1
broad band between 3600 and 3000 cm is attributed to
the stretching of O─H and N─H bonds. These results
show the MNPs were successfully coated with the poly-
mer. Following metal complexation, the intensities and
−
1
locations of the bands at 1400 and 1120 cm
were
changed. The intensity of the peak at approximately
FIGURE
MNP@PAMPS‐Pd(II)
4
TGA curves of (a) MNP@PAMPS and (b)
−
1
1
400 cm
assigned to the stretching of C─N band
became weaker than that for MNP@PAMPS, and the
−
1
band was shifted to lower wavenumber, 1398 cm , due
to the coordination of palladium ions to the ligand via
donor nitrogen atoms. An apparent intensity decrease
decomposition step (under 200 °C) corresponds to the
removal of physically adsorbed water. The second step of
weight loss (about 220–295 °C) is related to the decomposi-
tion of sulfonate groups, associated with PAMPS.
third thermal degradation at about 400 °C is ascribed to
−
1
[48]
was recorded for the band at 1120 cm due to asymmet-
The
−
1
ric ─SO stretching and a shift to 1116 cm , indicating
2
the occurrence of the palladium complex (Figure 2d).
main‐chain degradation of immobilized polymer on the
[
48]
surface of MNPs.
According to Figure 4(a), the amount
of organic components loaded on the surface of MNPs can
be calculated approximately. The observed total weight
loss between 200 and 800 °C for MNP@PAMPS is 26%,
which is attributed to the polymeric moieties. Comparing
3
.1.2 | XRD analysis
The XRD pattern of the supported palladium catalyst
exhibits diffraction peaks at around 30.5°, 35.9°, 43.5°,
[
49]
5
3.9°, 57.2° and 63° (2θ) ascribed to the inverse cubic spi-
with the TGA curve of AMPS,
the thermal stability of
nel structure of Fe O , which is consistent with the stan-
the magnetic polymer is intensified markedly, which is
possibly due to PAMPS chemically bonded to the surface
of the modified Fe O nanoparticles. A closer inspection
3
4
[47]
dard Fe O XRD pattern (Figure 3).
As illustrated in
3
4
Figure 3, the surface modification of the Fe O nanoparti-
3
4
3 4
cles did not lead to a phase change. Furthermore, no peak
characteristic for Pd nanoparticles was observed. So, the
XRD pattern confirms that the loading of Pd(ΙΙ) on the
catalyst was successful.
of the TGA curve of MNP@PAMPS‐Pd(II) shows slightly
lower thermal stability after the immobilization of palla-
dium ions, which can be due to the coordination of the
0
[
50]
metal ions with the ligands
and the catalytic effect of
palladium ions in the decomposition of the polymeric
[51]
structure.
Still, this thermal stability is very acceptable
3
.1.3 | Thermal analysis
for the catalyst application, such as C─C coupling reac-
tions, which are carried out at high temperatures. Also,
when compared to the percentage of the remaining mass
of MNP@PAMPS (ca 62%) (Figure 4a), MNP@PAMPS‐
Pd(II) has higher undecomposed content (ca 80%). This
difference can be attributed to the amount of loaded palla-
dium and polymeric moieties in the structure of the
catalyst.
The thermal degradation of MNP@PAMPS and
MNP@PAMPS‐Pd(II) was investigated using TGA to study
the composition and weight loss at different decomposition
temperatures of the desired nanocatalyst (Figure 4). Both
materials show three main decomposition stages. The first
3.1.4 | Vibrating sample magnetometry
In order to assay the effect of the polymeric moieties and
immobilization of palladium ions on the magnetic prop-
erties of the Fe O nanoparticles, the magnetic properties
3
4
of bare Fe O nanoparticles and MNP@PAMPS‐Pd(II)
3
4
were measured via VSM at room temperature (Figure 5).
FIGURE 3 XRD pattern of (a) Fe
MNP@PAMPS‐Pd(II)
3 4
O nanoparticles and (b)
As shown in Figure 5, the magnetic saturation value
markedly decreased to 30 emu g for MNP@PAMPS‐
−
1

ARGHAN ET AL.
7 of 16
placed beside a vial containing a suspension of
MNP@PAMPS‐Pd(II) nanocomposite spheres, the nano-
composites are quickly attracted to the side of the vial
within a few seconds (Figure 5, inset).
3
.1.5 | Field‐emission scanning electron
microscopy
The morphology and particle shape of MNP@PAMPS‐
Pd(II) were studied using FE‐SEM (Figure 6d). As can be
seen, the morphology of MNP@PAMPS‐Pd(II) is
[52]
completely different from those of the ligands
(Figure 6
FIGURE 5 Room temperature magnetization curves of (a) Fe
nanoparticles and (b) MNP@PAMPS‐Pd(II)
3 4
O
a,b) and Fe O nanoparticles (Figure 6c). These observa-
3
4
tions demonstrate that PAMPS was successfully linked to
Fe O nanoparticles and palladium ions were coordinated
3
4
Pd(II). This significant decrease may be assigned to the
fact that the Fe O nanoparticles were coated entirely by
an inert organic shell. However, the level of catalyst mag-
netization is still adequate, so that when a magnet is
with the ligands. The FE‐SEM image of MNP@PAMPS‐
Pd(II) (Figure 6d) illustrates that the catalyst particles are
quasi‐spherical. The image shows the presence of the com-
posite on the nanometre‐sized particles.
3
4
3 4
FIGURE 6 FE‐SEM images of (a) PAMPS, (b) P(AMPS‐co‐IA), (c) Fe O nanoparticles and (d) MNP@PAMPS‐Pd(II)

8
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ARGHAN ET AL.
FIGURE 7 EDX spectrum of MNP@PAMPS‐Pd(II)
3.1.6 | EDX analysis
MNP@PAMPS‐Pd(II) was analysed for its chemical com-
position through EDX analysis to verify the successful
incorporation of polymeric segments on Fe O surface
3
4
and palladium attachment to them. The EDX spectrum
Figure 7) indicated the presence of the Pd as well as C,
(
N, O, S and Fe in the body of the catalyst. The amount
of Pd(II) supported onto the PAMPS‐grafted modified
MNPs was determined as 7.7% (based on EDX results).
3.1.7 | Transmission electron microscopy
Further characterization of MNP@PAMPS‐Pd(II) was
performed using TEM. From the TEM images of
MNP@PAMPS‐Pd(II) (Figure 8), it could be seen that
the morphology of MNP@PAMPS‐Pd(II) remained almost
FIGURE 8 (a, b) TEM images of MNP@PAMPS‐Pd(II)
the same after loading Pd(OAc) on MNP@PAMPS.
reactions under green conditions have been reported.[55–57]
2
So, to investigate the performance of the catalyst, we evalu-
ated its catalytic activity in C─C coupling reactions, not only
for Suzuki–Miyaura cross‐coupling of aryl halides and
phenylboronic acid (Scheme 2), but also for Mizoroki–Heck
reactions of aryl halides and activated alkenes (Scheme 3).
3
.1.8 | ICP‐OES analysis
ICP‐OES analysis was used to explore the palladium con-
tent of the supported catalyst. The amount of palladium
in the catalyst was determined to be 0.73 mmol g which
is in good agreement with the result of EDX analysis.
−
1
3
.2.1 | Optimization of reaction parame-
3
.2 | Effectiveness of MNP@PAMPS‐
ters for Suzuki–Miyaura coupling reaction
Pd(II) in C─C Coupling Reactions
In the palladium‐catalysed Suzuki C─C coupling reac-
tions, parameters like the amount of the catalyst, solvent,
reaction time, temperature and base system are impor-
tant. So, these parameters should be optimized before
the catalytic activity determination is performed. The
effect of various parameters on Suzuki–Miyaura cross‐
coupling of iodobenzene with phenylboronic acid in the
presence our new catalytic system as a model reaction
was investigated and the results are as follows.
After the novel nanocomposite was fully characterized with
various techniques, its catalytic activity was studied in C─C
coupling reactions. A versatile polymer‐supported heteroge-
neous palladium catalyst for Mizoroki–Heck and Suzuki–
[53,54]
Miyaura reactions has been introduced.
But, to the best
of our knowledge, few successful examples of hydrophilic
polymer‐stabilized magnetically separable palladium mate-
rials to catalyse Suzuki–Miyaura and Mizoroki–Heck

ARGHAN ET AL.
9 of 16
SCHEME 2 MNP@PAMPS‐Pd(II)‐
catalysed Suzuki–Miyaura reaction
SCHEME 3 MNP@PAMPS‐Pd(II)‐
catalysed Mizoroki–Heck reaction
Effect of amount of MNP@PAMPS‐Pd(II) catalyst
To determine the suitable catalyst loading, the model
reaction was carried out with different amounts of the
catalyst added. The results are summarized in Table 1.
Initially, the model reaction was carried out in the
absence of the catalyst. As expected, no product was
observed in the absence of the catalyst. As can be seen,
as the amount of catalyst increased from 0.005 to
aryl halides, the choice of this solvent mixture provides
a good interaction between them, which leads to an
improvement in the Suzuki–Miyaura reaction.
Effect of base
Base is one part of the catalytic mechanism and it should
exhibit high efficiency and be of low cost. So, the reaction
is significantly affected by the nature of the base and the
additive used. Therefore, a variety of bases were evalu-
ated. As can be seen from Table 1, the best performance
occurred with K CO .
0
.01 mol%, the product yield increased, which is probably
due to the availability of more catalytic sites. According to
the results, 0.007 mol% was chosen as the optimum
amount of catalyst, affording the best product yield.
2
3
Effect of time and temperature
Effect of solvent
Temperature affects the kinetics of a reaction crucially.
Also, shorter reaction times are desired for catalysis sys-
tems to decrease labour and operational cost. Hence, in
order to investigate the effect of these two parameters,
the model reaction was carried out at different tempera-
tures for different times. According to Table 1, the best
choice was 80 °C as the optimal temperature when the
reaction continued for 30 min.
Solvents can allow thermodynamic and kinetic control
over a chemical reaction, so the choice of an appropriate
solvent is very important. Thus, the model reaction was
carried out in conventional solvents to obtain the best cat-
alytic conversion. As can be seen from Table 1, this reac-
tion proceeded faster, more cleanly and in higher yields
when the reaction was conducted in a mixture of H O
2
and EtOH in 1:1 ratio as solvent. Because of the hydro-
philic character of polymer‐stabilized palladium, water
solubility of boronic acid and hydrophobic character of
Consequently, the optimum reaction conditions were
determined as: 0.007 mol% of the catalyst
(MNP@PAMPS‐Pd(II)) in 5 ml of EtOH–H O (1:1) at
2
TABLE 1 Optimization of reaction conditions for Suzuki–Miyaura reaction of iodobenzene with phenylboronic acid catalysed by
MNP@PAMPS‐Pd(II)
Entry
Amount of catalyst (mol%)
Solvent
Temperature (°C)
Base
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
9
0
H
H
H
H
2
2
2
2
O
O
O
O
25
25
25
25
25
25
25
25
25
25
60
80
100
K
K
K
K
K
K
K
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
120
40
30
30
30
30
30
30
30
30
30
30
30
0
0.005
0.007
0.01
65
75
75
52
90
70
40
57
45
95
98
99
0.007
0.007
0.007
0.007
0.007
0.007
0.007
0.007
0.007
EtOH
O–EtOH (1/1)
CH COOEt
H
2
3
3
H
2
H
2
H
2
H
2
H
2
H
2
O–EtOH (1/1)
O–EtOH (1/1)
O–EtOH (1/1)
O–EtOH (1/1)
O–EtOH (1/1)
O–EtOH (1/1)
Na
2
CO
3
KOH
10
11
12
13
NaOH
K
K
K
2
2
2
CO
CO
CO
3
3
3

10 of 16
ARGHAN ET AL.
reflux temperature (80 °C) and 3.0 mmol of K CO as a
base in the reaction of iodobenzene (1.0 mmol) and phe-
nyl boronic acid (1.2 mmol).
performance of our new catalyst for the Mizoroki–Heck
reaction. In this regard, we first examined the factors
affecting the Heck reaction in order to achieve optimal
conditions. Iodobenzene and methyl acrylate were taken
as model substrates to optimize the reaction conditions.
2
3
3
.2.2 | Performance of catalyst with several
substrates for Suzuki–Miyaura reaction
Effect of amount of MNP@PAMPS‐Pd(II) catalyst
Our efforts were focused on optimizing conditions for
C─C coupling reaction of iodobenzene with methyl acry-
late by using different amounts of MNP@PAMPS‐Pd(II)
to determine their effects on the reaction (Table 3). As
can be seen, as the amount of catalyst increased from
After the optimization of the reaction conditions, to
explore the scope of this reaction and screen the effi-
ciency of our novel nanocatalyst, we extended the sub-
strate scope to various aryl halides (aryl bromides, aryl
chlorides and aryl iodides) with phenylboronic acid for
the Suzuki–Miyaura reaction (Scheme 2). These findings
are summarized in Table 2. In most cases, good to
excellent yields were obtained. It is noteworthy that aryl
chloride reacts with more difficult and in longer reac-
tion times compared to aryl bromide and aryl iodide.
This difference is due to stronger C─Cl bond than C─Br
and C─I, or, in other words, chlorides have high bond
dissociation energy. Turnover number (TON) and turn-
over frequency (TOF) were calculated for all products
as listed in Table 2. As can be seen, the catalyst yielded
remarkable TONs and TOFs.
0.005 to 0.03 mol%, the product yield increased from 55
to 95%, which is probably due to the availability of more
catalytic sites. According to the results, 0.02 mol% was
chosen as the optimum amount of catalyst, affording the
best yield.
Effect of solvent
In order to investigate the effect of solvents, the model
reaction was carried out in conventional organic solvents
such as DMF, EtOH, H O, MeOH and DMSO at 85 °C.
2
According to the results in Table 3, DMF is the best sol-
vent for the reaction.
Effect of base
3
.2.3 | Optimization of reaction parame-
The utilization of a base in the Mizoroki–Heck reaction is
essential to neutralize hydrogen halides and prevent
homo‐coupling product formation.
ters for Mizoroki–Heck reaction
[
42]
Following the excellent results obtained for the Suzuki–
So, the effect of dif-
Miyaura reaction, we were encouraged to examine the
ferent bases for the model reaction was further
a
TABLE 2 Effect of MNP@PAMPS‐Pd(II) on coupling of aryl halides with PhB(OH)
2
b
c
d
d
Entry
Aryl halide
Product
Time (min)
Yield (%)
M.p. (°C)
TON
TOF
1
30
99
69
14 143
13 143
13 571
12 857
14 000
13 714
8 571
28 286
26 286
20 255
17 143
28 000
23 645
4 286
2
3
4
5
6
7
30
40
45
30
35
120
60
92
95
90
98
96
60
50
87–90
70
45–47
111–113
82–85
69
e
8
69
7 143
7 143
a
2 3 2
Reaction conditions: aryl halide (1.0 mmol), phenylboronic acid (1.2 mmol), K CO (3 mmol), catalyst (0.007 mol%) and EtOH–H O (1:1) (5 ml), at 80 °C.
b
Detected by TLC.
c
Isolated yield.
d
TON, turnover number: yield of product per mole of Pd. TOF, turnover frequency: TON/time of reaction (h).
e
In the presence of excess mercury.

ARGHAN ET AL.
11 of 16
TABLE 3 Optimization of reaction conditions for Mizoroki–Heck reaction of iodobenzene with methyl acrylate catalysed by
MNP@PAMPS‐Pd(II)
Entry
Amount of catalyst (mol%)
Solvent
Temperature (°C)
Base
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
9
0.005
0.01
0.02
0.03
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
DMF
DMF
DMF
DMF
DMSO
MeOH
85
85
85
85
85
85
85
85
85
85
85
70
100
110
K
K
K
K
K
K
K
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
70
70
40
35
50
60
60
60
60
60
60
60
40
35
55
60
95
95
87
80
50
58
90
75
40
90
98
98
H
2
O
3
EtOH
DMF
DMF
DMF
DMF
DMF
DMF
Na
2
CO
3
KOH
1
1
1
1
1
0
1
2
3
4
NaOH
K
K
K
K
2
2
2
2
CO
CO
CO
CO
3
3
3
3
investigated. As can be seen from Table 3, the best perfor-
mance occurred with K CO .
reactions in comparison with other aryl halides (aryl bro-
mide and aryl iodide) because they are inexpensive and
widely available. Therefore, their use in coupling reac-
tions is significant. Most reported methods require harsh
conditions and high loadings of palladium catalyst. Nev-
ertheless, those catalysts show little or no activity with
aryl chloride substrates. In contrast, in the present
method, Mizoroki–Heck coupling of even less reactive
aryl chloride with olefin gives good yield as evident from
Table 4. As is clear from Table 4, the achieved TONs and
TOFs are very favourable.
2
3
Effect of temperature
Because of the importance of temperature for the
Mizoroki–Heck reaction, after the optimization of other
parameters, the model reaction was investigated at various
temperatures. According to Table 3, the best performance
in terms of high yield occurred at 100 °C. Thus, 100 °C was
considered as an optimum reaction temperature.
Consequently, the optimum reaction conditions for
the Mizoroki–Heck reaction were determined as:
0
.02 mol% of the catalyst (MNP@PAMPS‐Pd(II)) in 3 ml
of DMF at 100 °C and 2.0 mmol of K CO as a base in
the reaction of iodobenzene (1.0 mmol) and methyl acry-
late (1.5 mmol).
2
3
3
.3 | Comparison of Results Using
MNP@PAMPS‐Pd(II) With Results
Obtained by Other Workers for the
Mizoroki–Heck and Suzuki–Miyaura
Reactions
3.2.4 | Performance of catalyst with sev-
eral substrates for Mizoroki–Heck reaction
The efficiency of the MNP@PAMPS‐Pd(II) catalyst in the
Suzuki–Miyaura reaction (Table 5) and the Mizoroki–
Heck reaction (Table 6) was compared with that of some
previously reported palladium‐supported catalysts. Pres-
ent protocol and catalyst have the advantages of magnetic
recyclability, using a small amount of the catalyst, shorter
reaction time, using a green solvent without any additional
instrumentation such as a microwave oven, and high prod-
uct yield. Therefore, it can be seen that MNP@PAMPS‐
Pd(II) is a very beneficial and advantageous catalyst in
the Mizoroki–Heck and Suzuki–Miyaura reactions.
In the final step, to broaden the scope of this new proto-
col, the Mizoroki–Heck reaction was carried out by
employing various aryl halides with a variety of olefins
(Scheme 3). As is evident from Table 4, almost all reac-
tions gave good to excellent yields. The results show that
aryl chloride reacts more slowly than aryl bromide and
aryl iodide. Since oxidative addition is the first step in cat-
alytic coupling reactions, it is not favoured with aryl chlo-
ride substrates because of the high strength of the C─Cl
bond. Aryl chlorides are an ideal substrate for coupling

12 of 16
ARGHAN ET AL.
a
TABLE 4 Mizoroki–Heck coupling reactions of aryl halides with olefins
b
c
d
d
Entry
Aryl halide
Olefin
Product
Time (min)
Yield (%)
M.p. (°C)
TON
TOF
1
40
98
35–39
4 900
4 750
4 750
7 424
5 722
7 196
2
3
50
40
95
95
34–38
83–86
4
45
96
60–63
4 800
6 400
5
6
7
120
40
73
97
94
35–39
3 650
4 850
4 700
1 825
7 348
6 266
140–142
140–142
45
a
2 3
Reaction conditions: aryl halide (1.0 mmol), olefin (1.5 mmol), K CO (2.0 mmol), catalyst (0.02 mol%) and DMF (3 ml), at 100 °C.
b
Detected by TLC.
c
Isolated yield.
d
TON, turnover number: yield of product per mole of Pd. TOF, turnover frequency: TON/time of reaction (h).
TABLE 5 Comparison of results using MNP@PAMPS‐Pd(II) with those obtained using other catalysts for Suzuki–Miyaura reaction
Entry
Catalyst
Conditions
Time (h (min))
Yield (%)
Ref.
[
[
[
[
[
58]
59]
46]
60]
61]
1
2
3
4
5
6
7
8
Pd‐imino‐Py‐γ‐Fe
2
O
3
100 °C/DMF
100 °C/PEG
(30)
(40)
2
95
Pd‐ATBA‐MNPs
97
GO/Fe
3
O
4
/PAMPS/Pd
80 °C/EtOH–H
80 °C/EtOH–H
2
2
O
O
100
99
Pd/CNFs
4
Pd@CC‐SO
3
H‐NH
100 °C/H
25 °C/H
Reflux/MW, EtOH
80 °C/EtOH–H
2
O
2
96
3
[62]
63]
[κ ‐N,N′,O‐Pd(1 ⊂ 2)H
2
O]OAc
2
O
(35)
(30)
(30)
84
[
Pd/Fe
3
O
4
@SiO
2
99.7
99
MNP@PAMPS‐Pd(II)
2
O
This work
[
[
[
[
64]
65]
66]
67]
9
γ‐Fe
2
O
3
‐Pd
110 °C/DMF–H
2
O
2
90
71
64
59
90
1
1
1
1
0
1
2
3
rGO/Pd (0.5)
60 °C/EtOH–H
2
O
1(30)
(4)
Chitosan‐supported Pd
CL‐St‐Pd
50 °C/MW, solvent‐free
CL‐St‐Pd
(6)
MNP@PAMPS‐Pd(II)
80 °C/EtOH–H
2
O
(45)
This work
3
.4 | Recyclability of MNP@PAMPS‐Pd(II)
Suzuki–Miyaura reaction of iodobenzene with
phenylboronic acid as the model reaction. The catalyst
after the first cycle of the reaction was simply taken out
with a permanent magnet and washed several times with
The reusability of the MNP@PAMPS‐Pd(II) catalyst was
investigated under the optimized conditions for the

ARGHAN ET AL.
13 of 16
TABLE 6 Comparison of results using MNP@PAMPS‐Pd(II) with those obtained using other catalysts for the Mizoroki–Heck reaction
Entry
Catalyst
Conditions
Time (h (min))
Yield (%)
Ref.
[
[
68]
69]
1
2
3
4
5
6
7
Thiophene‐based iminopyridyl Pd(II) complexes
110 °C/DMF
110 °C/DMF
80 °C/DMF–H
100 °C/DMA
100 °C/DMA
120 °C/aq. CH
100 °C/DMF
8
69
95
91
95
99
99
98
[Pd(1‐tritylimidazole)
2
Cl
2
]
12
6
a
[70]
[Pd‐BOX‐Si]
2
O
[
[
71]
71]
Pd/CoBDC
9
Pd/CoBDCNH
2
9
b
[72]
Pd@ZPGly
3
CN 84%
3
MNP@PAMPS‐Pd(II)
(40)
This work
[
[
[
[
59]
73]
74]
75]
8
9
Pd‐ATBA‐MNPs
120 °C/PEG
120 °C/DMF
120 °C/DMF
8(20)
1(30)
4
86
95
60
75
94
Pd(0)‐ABA‐Fe
Fe @CS‐Schiff base Pd
ZrO @ECP‐Pd
MNP@PAMPS‐Pd(II)
3 4
O
1
1
1
0
1
2
3 4
O
2
120 °C/[bmim]PF
100 °C/DMF
6
3
(45)
This work
a
Silica‐supported palladium‐bis(oxazoline).
b
Palladium nanoparticles on zirconium carboxyaminophosphonate nanosheets.
deionized water and ethanol, dried in an oven at 60 °C
and reused for further catalytic cycles directly. As can be
seen from Figure 9, the catalyst maintained its activity
with no significant decrease in the yield up to six runs.
Loss of the catalyst during washing could be a reason
for the slight decrease of the yield. Changes in the chem-
ical structure of the recycled catalyst were investigated
using FT‐IR spectroscopy, FE‐SEM and EDX analysis.
Figure 10 shows the FT‐IR spectra of MNP@PAMPS‐
Pd(II) before and after the catalyst was used six times in
the reaction medium. As seen in Figure 10, no significant
change in the FT‐IR spectrum of the catalyst was
observed after six cycles. Moreover, using FE‐SEM
(Figure 11), the character of the recovered catalyst was
determined suggesting that the catalyst remained intact
and there was no change in the morphology during the
reaction and recycling stages as compared to the pristine
catalyst. In addition, the elemental composition
(Figure 12) shows the presence of C, N, O, S, Fe and Pd
in the nanocomposite structure. The content of palladium
in the recovered catalyst was determined as 7.67% (based
on EDX results).
FIGURE 9 Recyclability of MNP@PAMPS‐Pd(II) for Suzuki–
Miyaura reaction of iodobenzene with phenylboronic acid (reaction
conditions: iodobenzene (1.0 mmol), phenylboronic acid (1.2 mmol),
FIGURE 10 FT‐IR spectra of MNP@PAMPS‐Pd(II) (a) before use
K CO
2 3
2
(3 mmol), catalyst (5 mg) and EtOH–H O (1:1) (5 ml), at 80 °C)
and (b) after being reused six times

14 of 16
ARGHAN ET AL.
FIGURE 11 FE‐SEM images of MNP@PAMPS‐Pd(II) (a) before use and (b) after being reused six times
the reaction between iodobenzene and phenylboronic acid
was performed under the optimized conditions, and the
MNP@PAMPS‐Pd(II) catalyst was entirely removed from
the reaction mixture using an external magnet at approxi-
mately 50% conversion of the starting material (15 min).
Then, the reaction was allowed to stir for 2 h (and no fresh
catalyst was added) and no further reaction and increase in
the product yield occurred (monitored by TLC), which is
[50]
consistent with the heterogeneous nature of the catalyst.
4
| CONCLUSIONS
FIGURE 12 EDX spectrum of recovered MNP@PAMPS‐Pd(II)
1. The present work contributes to the development of a
novel effective magnetic polymer‐supported Pd(II)
catalyst.
3.5 | Mercury Poisoning Experiments
2
. The synthesis of PAMPS‐grafted modified MNPs with
a core–shell structure through a ‘grafting from’
approach was performed for the first time, and they
The most commonly accepted method of assessing cata-
lytic nature (heterogeneous or homogeneous) is the mer-
[22]
cury poisoning test.
If a catalyst is heterogeneous, the
were effectively employed as
immobilizing palladium acetate.
a
scaffold for
most important factor is the surface. If the surface of the
catalyst is blocked, no reaction will occur. So, if the cat-
alytic activity is stopped by adding mercury, the catalyst
has a heterogeneous nature. But a homogeneous catalyst
3. PAMPS acted as a bidentate ligand, through oxygen
and nitrogen atoms, so no additional ligand was
added.
4. The supported catalyst was confirmed using several
analytical techniques including FT‐IR spectroscopy,
XRD, TGA, TEM, VSM, FE‐SEM, ICP‐OES and EDX
analysis.
[50]
is not affected by the presence of mercury.
The results
showed that the catalyst was poisoned and lost its activ-
ity upon addition of mercury, indicating that the reaction
mechanism had a heterogeneous nature (Table 2, entry 7).
5
. Leaching and mercury tests confirmed the lack of
metal leaching and the heterogeneity of the catalyst,
respectively.
3.6 | Leaching
To determine the amount of palladium leaching, another
catalytic experiment was carried out. For this purpose,
6. Simple catalyst preparation, easy magnetic recyclabil-
ity and reusability, reusable several times without loss

ARGHAN ET AL.
15 of 16
of activity and high thermal stability are some of the
advantages of the protocol presented.
[16] F. Havasi, A. Ghorbani‐Choghamarani, F. Nikpour, New J.
Chem. 2015, 39, 6504.
7
. The resulting catalyst proved to be a highly efficient
heterogeneous catalyst for the Mizoroki–Heck and
Suzuki–Miyaura reactions affording excellent yields
and remarkable TONs and TOFs. The methodology
developed for the mentioned reactions was cost‐effec-
tive, eco‐friendly and simple.
[17] L. Fernández‐García, M. Blanco, C. Blanco, P. Álvarez, M.
Granda, R. Santamaría, R. Menéndez, J. Mol. Catal. A 2016,
416, 140.
[18] M. Semler, J. Čejka, P. Štěpnička, Catal. Today 2014, 227, 207.
[19] S. Rostamnia, E. Doustkhah, B. Zeynizadeh, J. Mol. Catal. A
2016, 416, 88.
[
20] S. Rostamnia, H. Xin, Appl. Organomet. Chem. 2013, 27, 348.
21] T. Baran, I. Sargin, M. Kaya, A. Menteş, Carbohydr. Polym.
[
2
016, 152, 181.
ACKNOWLEDGEMENT
[
[
22] T. Baran, A. Menteş, J. Organomet. Chem. 2016, 803, 30.
The authors acknowledge Semnan University Research
Council for supporting this work.
23] S. Ghosh, R. Dey, S. Ahammed, B. C. Ranu, Clean Technol.
Environ. 2014, 16, 1767.
[24] J. Chung, J. Kim, Y. Jang, S. Byun, T. Hyeon, B. M. Kim, Tetra-
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ORCID
[
[
[
25] S. Keshipour, S. Shojaei, A. Shaabani, Cellul. 2013, 20, 973.
26] Z. Dong, Z. Ye, Appl. Catal. A 2015, 489, 61.
Maryam Arghan http://orcid.org/0000-0003-1447-1615
Nadiya Koukabi http://orcid.org/0000-0002-7358-783X
Eskandar Kolvari http://orcid.org/0000-0003-0484-5273
27] M. Bhardwaj, S. Sahi, H. Mahajan, S. Paul, J. H. Clark, J. Mol.
Catal. A 2015, 408, 48.
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