Green synthesis and characterization of palladium nanoparticles supported on zeolite Y by sonochemical method, powerful and efficient catalyst for Suzuki-Miyaura coupling of aryl halides with phenylboronic acid

Article abstract of DOI:10.1002/aoc.4594

In this paper, we report effective, useful and environmental compatible ultrasound method for the synthesis of zeolite–Y. Then, the prepared product was composed with palladium nanoparticles by sonication treatment. The prepared zeolite Y–Pd nanoparticles was used as catalyst in Suzuki-Miyaura coupling of aryl halides (Ar-X, X?=?I, Br, Cl, F) with phenylboronic acid. Based on our studies, the prepared zeolite Y-Palladium nanoparticles revealed a high catalytic performance in Suzuki-Miyaura coupling reaction so that aryl fluoride can even react with phenylboronic acid by utilizing this catalyst. The advantages of the use of this catalyst in Suzuki-Miyaura coupling reaction are green solvent, short reaction time, high yields, ligandless and recyclable. Structure and morphology of the synthesized zeolite-Y and zeolite-Y-Palladium nanoparticles were characterized by FT-IR (Fourier transform infrared), XRD (X-ray diffraction), SEM (Scanning electron microscopy), TEM (Transmission electron microscopy), EDX (Energy dispersive analysis of X-ray), BET (Brunauer Emmett Teller) and ICP-MS (Inductively coupled plasma mass spectrometry).

Full text of DOI:10.1002/aoc.4594

Received: 26 May 2018
DOI: 10.1002/aoc.4594
Revised: 6 August 2018
Accepted: 17 August 2018
F U L L P A P E R
Green synthesis and characterization of palladium
nanoparticles supported on zeolite Y by sonochemical
method, powerful and efficient catalyst for Suzuki‐Miyaura
coupling of aryl halides with phenylboronic acid
Azadeh Tadjarodi
| Modarres Dehghani | Mina Imani
Research Laboratory of Inorganic
In this paper, we report effective, useful and environmental compatible ultra-
sound method for the synthesis of zeolite–Y. Then, the prepared product was
composed with palladium nanoparticles by sonication treatment. The prepared
zeolite Y–Pd nanoparticles was used as catalyst in Suzuki‐Miyaura coupling of
aryl halides (Ar‐X, X = I, Br, Cl, F) with phenylboronic acid. Based on our
studies, the prepared zeolite Y‐Palladium nanoparticles revealed a high cata-
lytic performance in Suzuki‐Miyaura coupling reaction so that aryl fluoride
can even react with phenylboronic acid by utilizing this catalyst. The advan-
tages of the use of this catalyst in Suzuki‐Miyaura coupling reaction are green
solvent, short reaction time, high yields, ligandless and recyclable. Structure
and morphology of the synthesized zeolite‐Y and zeolite‐Y‐Palladium nanopar-
ticles were characterized by FT‐IR (Fourier transform infrared), XRD (X‐ray
diffraction), SEM (Scanning electron microscopy), TEM (Transmission electron
microscopy), EDX (Energy dispersive analysis of X‐ray), BET (Brunauer
Emmett Teller) and ICP‐MS (Inductively coupled plasma mass spectrometry).
Materials Synthesis, Department of
Chemistry, Iran University of Science and
Technology, Narmak, Tehran, Iran
Correspondence
Azadeh Tadjarodi, Research Laboratory of
Inorganic Materials Synthesis,
Department of Chemistry, Iran University
of Science and Technology, Narmak,
Tehran, Iran.
Email: tajarodi@iust.ac.ir
KEYWORDS
carbon–carbon cross coupling, palladium nanoparticles, Sonochemical method, zeolite Y
1
| INTRODUCTION
Faujasite family, has been widely used as industrial cata-
lyst for several commercial processes, as long‐chain hydro-
[7]
Zeolites are considered as hydrated aluminosilicates com-
posed of crystalline structure with molecular sieving prop-
erties. These compounds are inorganic materials with
thermal, chemical and mechanical stability and have been
carbon cracking and hydro processing technology.
Recently, the use of ultrasonic irradiation has been
[1]
[8–11]
extensively studied,
as a new source of energy and
environmentally compatible. The role of ultrasonic waves
in improvement of the formation of zeolite in different
[2,3]
[4]
widely used as catalysts,
ion exchangers and adsor-
[5]
[12]
[13]
bents. Faujasite (FAU) is one of the zeolite minerals,
which is widely used. Its structural framework can be
described in terms of a linkage of TO4 tetrahedral
heterogeneous
and homogeneous systems
is as
well‐known as its general contribution to the crystalliza-
[
14]
tion of distinct mineralogical phases.
Ultrasound has
(
T = Si, Al) in a truncated octahedron in a diamond‐type
been successfully used with the sol–gel process in the syn-
thesis of a wide range of nano and micro particles. The
[6]
structure. Zeolite Y, a highly versatile member of the
Appl Organometal Chem. 2018;e4594.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
1 of 10
https://doi.org/10.1002/aoc.4594

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TADJARODI ET AL.
use of ultrasonic treatment in synthesis reactions offers
several practical advantages compared to the conven-
tional methods due to the low reaction temperature and
improve the formation of product. This method is intro-
duced as a powerful technique to produce various mate-
rials in higher yields, shorter reaction times and milder
conditions. It can also assist in conservation of energy
and minimization of wastes compared to conventional
[15]
the short reaction time.
In fact, the ultrasound tech-
nique has been increasingly reported for the synthesis of
various functional materials due to unique activations
based on a physical phenomenon known as acoustic cav-
itation. The acoustic cavitations are generated during
passing the ultrasound waves through a liquid medium
and interacting with gas bubbles existing in the liquid.
The recent findings have indicated an accurate estimation
of temperatures and chemical events of acoustic bubbles.
They behave as special microreactors with high tempera-
ture and energy, which can increase reaction rates. It was
suggested that the ultrasonic technique with the forma-
tion of cavitation bubbles provides a mechanical force
with a high energy in the liquid phase and also acceler-
ates ionic reactions, molecular diffusion and mass
transfer. The ultrasonic treatment enhances reactivity
and assists in the breakdown of intermediates, dispersion
of particles in a finely divided form. In fact, the created
energy by ultrasound irradiation causes the chemical
effects in the irradiated liquid; formation, growth and
implosive collapse of bubbles, which increase and
[
16,17]
heating methods.
Also the ultrasound technique as
a reduction method has been used to prepare palladium
[
18]
nanoparticles from their salts.
Recently, the use of
ultrasound in the synthesis of micrometer sized (e.g. Na‐
[
19]
[20]
[11]
A,
Na‐P,
Na‐X,
MCM‐22 ) and nanometer‐sized (e.g.
[
21]
[22]
[23]
[24]
Na‐A,
silicalite‐1,
SAPO‐34 ) molecular
sieves has been reported. With this overview we also
introduced this procedure to synthesize functionalized
zeolite‐Y composite in this work.
The palladium‐catalyzed Suzuki‐Miyaura cross‐cou-
pling (Scheme 1) has become one of the most versatile and
powerful reactions for the construction of carbon–carbon
[
25]
bonds.
and substituted biaryls,
in the structures of natural products, agrochemicals, phar-
It is widely used in the synthesis of poly‐olefins
[
26]
which are important skeletons
[
27–29]
maceuticals, and advanced materials.
Generally,
phosphine ligands are often used in palladium‐catalyzed
processes but most of them are toxic, expensive and water
or air sensitive. Recently, the use of available aryl chlorides
FIGURE 1 General procedure for the
synthesis of Z‐Y‐Pd NPs catalyst
SCHEME 1 Zeolite Y‐Pd nanoparticles
catalyzed Suzuki–Miyaura coupling
reaction of aryl halide with phenylboronic
acid

TADJARODI ET AL.
3 of 10
and aryl fluorides in these transformations has received an
increasing attention so that a number of effective catalytic
systems have developed for this purpose.
We previously described an oil–water self‐assembly
strategy for the synthesis of Pd/reduced‐graphene oxide
and Pd nanoparticles at room temperature by reduction
radiation. The delivered power of ultrasound wave was
150 W. During sonication, the temperature of mixture
raised from ambient temperature to a steady state of
90 °C within 5 min by using a circulating oil bath. The
reactor temperature was kept constant at 90 °C (±1 °C).
After 3 h the resultant product was filtered, washed and
dried overnight at 80 °C.
[30]
of the [PdCl (cod)] complex and investigated their cata-
2
lytic activity in S‐M coupling reaction. These reported cat-
alysts showed a high performance in coupling reaction
with shorter time and higher yield compared to other
2
.2 | Zeolite Y‐palladium nanoparticles
(Z‐Y‐Pd NPs) catalyst preparation
[31]
catalysts.
In this work, an efficient sonochemical procedure is
reported for the synthesis of palladium nanoparticles sup-
ported on zeolite Y at rather low temperature of crystalli-
zation and short reaction time. The structural and
morphological characteristics of the resulting product
were studied by FT‐IR (Fourier transform infrared),
XRD (X‐ray diffraction), SEM (Scanning electron micros-
copy) EDX (Energy dispersive analysis of X‐ray) and ICP‐
MS (Inductively coupled plasma mass spectrometry). Our
catalytic studies on the S‐M reaction using the prepared
zeolite Y‐Pd nanoparticles showed this product is a suit-
able catalyst for carbon–carbon cross coupling (Suzuki‐
Miyaura coupling reaction).
The acid form of zeolite H‐Y was obtained by ion
exchange of NaY zeolite (1 g) with a solution of NH Cl
4
(1 M, 50 ml) at 80 °C for 4 h. After this process, the
exchanged zeolite was filtered, washed with deionized
water, dried at 120 °C overnight and then calcined at
500 °C for 4 hr. For the next step, 1 g of H‐Y zeolite
was added to 50 ml of ethylene glycol in a 100 ml
round‐bottom flask and then PdCl (0.04 g) and KOH
2
(0.45 g) were added to this solution. This mixture was dis-
persed by ultrasonic bath for 1 hr. After ultrasonic treat-
ment, product was filtered, washed and was kept
constant at 200 °C for 4 hr. The elemental analysis of
ICP‐MS was used to determine the percentage of the
loaded palladium on zeolite‐Y substrate.
2
| EXPERIMENTAL
2
.3 | General procedure for Suzuki–
Sodium hydroxide (NaOH, 99% wt., Merck), sodium alu-
minate (NaAlO , [Na O, 40–45%wt + Al O , 50–55%wt.]
Miyaura coupling reaction
2
2
2 3
Aryl halide (0.5 mmol) and phenylboronic acid
(Aldrich), NaSiO2 (Aldrich, Shanghai, China), PdCl2
(
0.75 mmol) were added to a flask containing the Z‐Y‐Pd
(Merck) and deionized water were used as received. Ultra-
NPs catalyst (15 mg) and K CO (1 mmol) in 10 ml dis-
tilled water and ethanol (1:1). The mixture was stirred in
an oil bath at 80 °C. After completion of the reaction
2
3
sound radiation was obtained by ultrasonic processor
FAPAN, 400R) with standard probe. The powder X‐ray
(
diffraction patterns (XRD) were obtained by a (STOE‐
STADV) instrument. Scanning electron microscopy
(SEM) images was obtained using a TESCAN instrument.
FT‐IR spectra were taken with a shimadzo spectrometer.
Brunauer Emmett Teller (BET) was obtained using a
Micromeritics ASAP 2020 instrument. TEM images were
1
obtained using a Zeiss‐EM10C‐100 KV instrument. H
NMR spectra were taken with a Bruker 400 MHz ultra‐
shield spectrometer using CDCl as the solvent and TMS
3
as the internal standard.
2.1 | Synthesis of zeolite NaY (Z‐Y)
Zeolite Y was prepared using a starting aluminosilicate
[
32]
gel with molar ratio 1Al O : 4Na O: 9SiO :170H O.
2
3
2
2
2
In a typical preparation, NaAlO (1.4 g), H O (18.1 ml),
2
2
NaOH (5.1 g), and SiO (17.3 ml) at room temperature
2
were mixed by stirring for 24–36 hr. Then the mixture
FIGURE 2 XRD patterns of the formation of Z‐Y at different
was subjected to conventional heating, ultrasound
times by sonochemical method (150w and 90 °C)

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TADJARODI ET AL.
TABLE 1 Synthesized zeolites with hydrothermal method
Entry
Time (h)
Temperature (°C)
Type of zeolite
Reference
1
2
3
4
5
6
7
48
100
90
50
150–200
96
Na‐Y
33
34
35
36
37
38
39
Na‐P
1
Blend
Na‐Y
Na‐Y
Na‐Y
Na‐Y
180
24
110
60
24
100
24
100
(
monitored by TLC), the reaction mixture was cooled
performed in short time, low temperature or pressure.
Furthermore, by gel composition and the use of ultra-
sonic, more convenient reaction conditions can be used
to form discrete and well‐defined zeolite nanoparticles.
This hence results in a significant improvement in nano-
crystal properties (electrical, optical, magnetic, catalytic,
etc.), which have an important impact on advanced appli-
down to room temperature, and then dichloromethane
was added to the reaction vessel. The organic phase was
separated and dried over anhydrous MgSO . The pure
desired product was obtained by the evaporation of the
solvent.
4
[
33–39]
cations and in fundamental studies.
In this study,
3
| RESULTS AND DISCUSSION
Pd nanoparticles have been prepared by the ultrasonic
reduction method. After ultrasonic treatment, the reduc-
tion of Pd (II) ions could occur by generated organic rad-
icals as the following reactions (1–3):
In this work, the synthesis of Z‐Y‐Pd NPs catalyst is
reported and it is suitable for Suzuki‐Miyaura cross cou-
pling reaction (Figure 1). At the first, we studied the effect
of time in synthesis of Z‐Y by sonochemical method.
Results showed that structure and morphology of Z‐Y as
shown in Figure 2 is completely formed at 3 hr by ultra-
sonic irradiation. XRD patterns confirmed the formation
of Z‐Y at different times with ultrasonic irradiations
•
•
H2O→ OH þ H
(1)
(2)
(3)
•
•
•
HOCH2CH2OH þ OHð HÞ→HOCH2C HOH
þ H2O ðH2Þ
(
150 W) at 90 °C. After crystallization, product shows
sharp diffraction peaks at 2 theta of 6.05°, 10.02°, 11.7°,
5.4°, 20.1°, 23.3°, 26.7° and 30.9°. This pattern confirms
•
1
nPd ðIIÞ þ 2nHOCH C HOH→nPdð0Þ
2
þ
the formation of Z‐Y.
þ 2nHOCH CHO þ 2nH
2
A comparison of the ultrasonic method and hydro-
thermal method was given in Table 1. It shows the syn-
thesis of zeolites by hydrothermal method needs to
consume the high energy and more time (Table 1),
whereas the synthesis of zeolites by ultrasonic method is
The proposed mechanism correspond with report Okitsu
[
40]
et al.
In fact, the created energy by ultrasound irradia-
tion causes the chemical effects in the irradiated liquid;
formation, growth and implosive collapse of bubbles,
FIGURE 3 (a) FT‐IR spectrum and (b) SEM image of synthesized Z‐Y

TADJARODI ET AL.
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FIGURE 4 (a) XRD pattern and (b) SEM image of Z‐Y‐Pd NPs
which increase and improve the formation of
nanoparticles.
the decorated dark spots, which can be probably related
to Pd particles. The average diameter of the Z‐Y‐Pd NPs
is about 84 nm with the decorated Pd nanoparticles with
the average size of about 5 nm. This indicates desirability
of the ultrasonic method for adhering Pd NPs on the sur-
face of zeolite. Also, the average crystallite size of the as
prepared Pd nanoparticles were calculated by the Scherer
formula: D = 0.9λ/(β cos θ), where D represents the crys-
tallite size (nm), β is the full width of the diffraction line
at half the maximum intensity, λ represents the wave-
The FT‐IR spectrum and SEM image of the synthe-
sized Z‐Y were indicated in Figure 3. There are the strong
−
1
vibrations at 1002, 719, 567 and 460 cm in the FT‐IR
spectrum of product (Figure 3a). The characteristics
−
1
bands at 460, 567 and 1002 cm are assigned to T‐O
(
T = Si, Al) bending and Si‐O, Al‐O tetrahedral vibration,
[41,42]
respectively.
The SEM image (shown in Figure 3b)
revealed a uniform particulate morphology with an aver-
age particle size of 84 nm.
[
44]
length of X‐ray and θ is the Bragg angle.
The average
XRD pattern and SEM image of the prepared Z‐Y‐Pd
NPs were shown in Figure 4. There are diffraction peaks
at 2 theta of 40.04°, 46.63° and 67.99°, which are related
to the palladium nanoparticles decorated on zeolite.
The peaks at 2 theta of 6.04°, 13.64°, 17.58° and 28.44°
crystallite size of about 7 nm obtained for the prepared
product using XRD pattern and Debye–Scherrer equa-
tion. This value is much lower than the obtained particle
size of 84 nm resulted from TEM images for the Z‐Y‐Pd
particles. It returns to the difference of concept of the
crystallite size and particle size. A particle may be made
up of several different crystallites or just one crystallite
that in this case is equal to particle size. We often report
the particle size based on SEM and TEM images because
we can't exactly determine whether the particle is one
crystallite or composed of many compacted single crys-
tals. The observed difference between the obtained values
of XRD and TEM images can reveal that each particle of
the prepared product is a composed of small crystallites
with the average crystallite size of about 7 nm.
[
43]
are attributed to Z‐Y substrate confirming its structure
[41]
without any changes.
The chemical composition of the Z‐Y‐Pd NPs was
determined by elemental analysis of EDX and ICP‐MS,
confirming the presence of Pd NPs (2.7%) on the zeolite
body (Figure 5).
Figure 6 (a‐b) shows TEM images of the Z‐Y‐Pd NPs,
which includes a spherical morphology of product with
Nitrogen adsorption–desorption measurements were
carried out at −196 °C on a Micromeritics ASAP 2020
instrument to determine the Brunauer Emmett Teller
(
BET) surface area and to estimate the mesopore size dis-
tribution using the Barrett Joyner Halenda (BJH) calcula-
tion procedure. Before each measurement, samples were
evacuated 3 hr at 300 °C. The N adsorption‐desoprtion
2
isotherm curves for the synthesized Z‐Y‐Pd NPs
(
Figure 7) revealed a hysteresis loop in the range of
0
< P/P < 1, which is in a close accordance with the cat-
0
FIGURE 5 EDAX spectrum of the Z‐Y‐Pd NPs
egory of type II, which represents a porous nature of the

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TADJARODI ET AL.
FIGURE 6 (a, b) TEM images and (c) histogram of particle size distribution of Z‐Y‐Pd NPs
prepared product. BET analysis using nitrogen adsorp-
the Z‐Y‐Pd NPs catalyst, as determined by ICP‐MS, was
2.72 wt%.
tion–desorption experiments indicated the surface area
2
−1
3
−1
of 80.66 m g . The pore volume of 0.001 cm g was
determined by the t‐plot method. In addition, the micro-
pore diameter was obtained at about 14.79 nm using
BJH curve. Based on the BET results, the synthesized Z‐
Y‐Pd NPs possess a good porous surface that is necessary
to make it an effective catalyst.
The Suzuki‐Miyaura coupling reactions of aryl halides
with phenylboronic acid were investigated by employing
the Z‐Y‐Pd NPs as catalyst. The weight percent of Pd in
A series of reactions were performed with various
amounts of catalyst to test the reaction feasibility with
catalyst concentration (Table 2). The optimal amount of
the Z‐Y‐Pd NPs catalyst was determined by the reaction
of bromobenzene with phenylboronic acid at 80 °C.
Based on the Table 2, it is evident that an increase in
the amount of Z‐Y‐Pd NPs catalyst leads to an increase
in yield of the cross‐coupled product. The optimum
amount of the Z‐Y‐Pd NPs catalyst is 15 mg.
To study the effects of different solvents in our cata-
lytic system, the coupling of bromobenzene with
phenylboronic acid was performed in the presence of var-
ious solvents. The results of the reactions have been pre-
sented in Table 3. According to our study, when polar
solvents are used, better catalytic performance can be
achieved in product (Entry 1, 2). Also, aprotic solvents
(
Entries 5–7) have relatively less yields. The lowest con-
version (63%) was obtained with THF (Entry 4) and the
highest conversion was obtained with H O: EtOH (1:1)
2
(
Entry 3, 98%). K CO as a base and reflux at 80 °C were
2 3
used for optimizing the solvent of the reaction.
Table 4 shows the catalytic activity of Z‐Y‐Pd NPs for
various aryl halides (aryl iodide, aryl bromide, aryl chlo-
ride and even aryl fluoride) in cross coupling reaction.
In these reactions, aryl iodide and bromide with various
FIGURE 7 Adsorption–desorption isotherm from Z‐Y‐Pd NPs

TADJARODI ET AL.
7 of 10
TABLE 2 Investigating the effect of catalyst amount in the synthesis of biphenyl from bromobenzene and phenylboronic acid at 80 °C in
O: EtOH
H
2
a
Entry
Amount of catalyst (mol %)
Yields (%)
1
2
3
4
0.007
0.01
0.02
0.04
73
90
98
98
a
Isolated yields.
TABLE 3 Suzuki–Miyaura coupling reaction in various solvents in the presence of 0.02 mol% of Pd NPs
a
Entry
Solvent
Yields (%)
1
2
3
4
5
6
7
EtOH
94
88
98
78
72
65
63
2
H O
EtOH:H
DMF
2
O (1:1)
DMSO
Toluene
THF
a
Isolated yields.
a
TABLE 4 Suzuki reaction of different aryl halides, with phenylboronic acid
b
Entry
Substrate
Product
Time (h): Yield (%)
1
2
3
4
5
6
7
8
9
C
C
C
6
6
6
H
H
H
5
5
5
I
a
a
a
b
c
0.25: 99
1.0: 98
1.5: 88
1.0: 98
2.5: 99
2.0: 91
2.0: 92
3.0: 63
2.5: 89
Br
Cl
6 4
4‐MeC H I
4‐NO
2
2
C
C
6
6
H
4
4
Br
Cl
4‐NO
H
c
4‐CNC
6
6
H
H
4
4
Cl
F
d
d
e
4‐CNC
5 4
C H NCl
a
2 3
Aryl halide (0.5 mmol), phenylboronic acid (0.75 mmol), Z‐Y‐Pd NPs (0.02 mol%), K CO (1.0 mmol), and water/ethanol (1:1, v/v).
b
Isolated yields.

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TADJARODI ET AL.
TABLE 5 Catalytic performance of different Pd‐based catalysts in the coupling of chlorobenzene and phenyl boronic acid
Entry Catalyst
Solvent
Base
Cs CO
PO
Temp (°C)
Time (h) Yield (%) References
[
[
[
[
[
[
[
[
[
[
[
[
46]
1
2
3
4
5
6
7
8
9
1
1
1
1
CelFemImiNHC@Pd complex EtOH
2
3
RT
2.0
5.5
0.5
1.5
2.0
3.0
2.5
3.0
6.0
12.0
0.5
54
47]
IPrPdCl
2
H
H
H
H
H
H
H
2
2
2
2
2
2
2
O/i‐PrOH
O/EtOH
O
K
K
K
K
K
K
K
K
K
3
2
2
2
2
2
2
2
2
4
RT
99
48]
Pd/3‐ampy‐GO
PtPdCu
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
80
85
45]
Reflux
80
49]
PdPtZn
O‐CTAB
O
Reflux
80
31]
Pd/r‐GO
Reflux
80
30]
Pd/Fe
Fe /P (GMA‐AA‐MMA)–Pd
PdCl
3
O
4
/r‐GO
O
Reflux
85
50]
3
O
4
O/EtOH
80
9
51]
2
PEG
RT
98
52]
0
1
2
3
Pd‐1/FSG
H
2
O
100
26
53,54]
54,55]
Pd/C (1% mol)
Pd/C (1% mol)
Z‐Y‐Pd NPs
TBAB,H
TBAB,H
2
2
O
O
Na
2
2
CO
3
3
Microwave heating, 120 °C
48–94
80–90
88
Na
CO
Microwave heating, 120–150 °C 0.2
Reflux 1.5
H
2
O/EtOH
K
2
CO
3
This work
substituents give excellent yields with conversions rang-
ing from 98 to 99% (Entries 1, 2, 4 and 5). Also, when
the aryl chloride substrates are used, good efficiency is
achieved with conversions ranging from 88 to 92%
the same conditions specially by utilizing CNC H F sub-
6 4
strate and monitored the progress of process by TLC.
The results did not show any progress in coupling reac-
tion after several hours, which can reveal the role of cat-
alyst in the progress of mentioned reactions.
(Entries 3, 6, 7 and 9). An interesting case with this cata-
lyst is the reaction between an inactive fluorine substrate
with phenylboronic acid (Entry 8) with conversion 63%.
To the best our knowledge there are a few catalyst that
able to react with aryl fluorides. A frequent observation
in Suzuki‐Miyaura coupling reaction states that a better
conversion is achieved with aryl halides containing an
We compared our results with those of noble metal‐
based catalysts reported in the past few years for
Suzuki‐Miyaura reactions, taking the reaction of chloro-
benzene with phenylboronic acid as an example
(Table 5). As shown, catalytic performance of Z‐Y‐Pd
NPs synthesized by ultrasonic treatment is excellent dur-
ing short time and more yield in compare with different
methods and catalysts.
The reusability of the Z‐Y‐Pd NPs catalyst was tested
for the reaction of bromobenzene and phenylboronic
acid. The catalyst was separated from the reaction mix-
ture by centrifugation, washed with ethyl acetate and
dried at room temperature and then reused in another
reaction with same materials of previous reaction. It
was found that the Z‐Y‐Pd NPs catalyst could be recycled
for ten times without losing the catalytic activity
[31]
electron‐withdrawing group.
For example, when aryl
halide containing a cyanide group, electron‐withdrawing
group, yield of reaction is better than when it involves
methyl group, electron‐donating group. The oxidative
addition of palladium into a carbon–halogen (C‐X) bond
occurs in the order I > Br > Cl > F, based mainly on
[45]
the strength of the C‐X bond.
In addition, we carried
out S‐M reaction without using the prepared catalyst in
(
Figure 8).
4
| CONCLUSIONS
In summary, a simple and green sonochemical method
was applied to synthesize zeolite Y and then, palladium
nanoparticles were deposited on the prepared zeolite Y
with ultrasonic treatment. The catalytic performance of
Z‐Y‐Pd NPs, we studied for the Suzuki‐Miyaura coupling
reaction. The Z‐Y‐Pd NPs showed a high activity in the
carbon–carbon coupling reaction that even aryl fluoride
FIGURE 8 Reusability of Z‐Y‐Pd NPs catalyst in the Suzuki‐
Miyaura cross‐coupling reaction between bromobenzene and
phenylboronic acid
revealed
a
rather good yield for reaction with

TADJARODI ET AL.
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phenylboronic acid in presence of this catalyst. This work
introduces the advantages of green solvent, short reaction
time, high yields, ligand‐free and reusability of the
catalyst.
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We gratefully acknowledge Iran University of Science
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−
1
6
1
9–71 °C); FT‐IR (KBr/cm ): 3030,1569, 1477, 1424,
1
[14] M. Run, G. Wu, Chin. J. Inorg. Chem. 2004, 20, 219.
167,1008, 731, 695; H NMR (400 MHz, CDCl3):
[
15] C. Belviso, F. Cavalcante, A. Lettino, S. Fiore, Ultrason.
δ = 7.46 (m, 2H), 7.55 (m, 4H), 7.71 (m, 4H).
‐Methylbiphenyl (b). [28] White solid, mp: 44–46 °C
Sonochem. 2011, 18, 661.
4
−
1
[16] M. F. Mady, A. A. El‐Kateb, I. F. Zeid, K. B. Jørgensen, J. Chem.
2013, 364036, 1.
(
lit. mp44–46 °C); FT‐IR (KBr/cm ): 3077, 3024, 2924,
1
2
851, 1603, 1438, 1348, 1123, 1019, 700; H NMR
[
17] M. Ashokkumar, Ultrasonic Synthesis of Functional Materials,
SpringerBriefs in Molecular Science, University of Melbourne,
Parkville, VIC Austral 2016.
(
400 MHz, CDCl ): δ = 2.45 (s, 3H, CH ), δ = 7.33 (m,
3
3
2
H), 7.37 (m, 1H), 7.59 (m, 2H), 7.76 (m, 2H), 7.88 (2H).
‐Nitrobiphenyl (c). [28] Yellow solid, mp: 112–115 °C
4
−
1
[18] A. Nemamcha, J. L. Rehspringer, D. Khatmi, J. Phys. Chem B.
006, 110, 383.
(lit. mp113–115 °C); FT‐IR (KBr/cm ): 3100, 3021, 1610,
2
1
1
578, 1441, 1310, 1089, 1024, 703; H NMR (400 MHz,
[
19] R. Herrmann, W. Schwieger, O. Scharf, C. Stenzel, H. Toufar,
M. Schmachtl, B. Ziberi, W. Grill, Microporous Mesoporous
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CDCl ): δ = 7.47 (m, 3H), 7.67 (m 2H), 7.77 (m, 2H),
3
8
.46 (m, 2H).
‐Phenylbenzonitrile (d). [28] White solid, mp:
4
[
[
[
[
20] N. M. Musyoka, L. F. Petrik, E. Hums, H. Baser, W. Schwieger,
−
1
8
4–87 °C (lit. mp84–88 °C); FT‐IR (KBr/cm ): 3046,
Ultrasonics 2014, 54, 537.
1
3
024, 2229, 1650, 1600, 1441, 1346, 1083, 1024, 703; H
21] P. Pal, J. K. Das, N. Das, S. Bandyopadhyay, Ultrason.
Sonochem. 2013, 20, 314.
NMR (400 MHz, CDCl ): δ = 7.53 (m, 3H), 7.63 (m,
3
2
H), 7.83 (m, 2H), 8.23 (m, 2H).
22] K. Shams, H. Ahi, Microporous Mesoporous Mater. 2013, 180,
2
‐Phenylpyridine (e). [28] Colorless oil, FT‐IR (KBr/
6
1.
23] H. Gürbüz, B. Tokay, A. E. Senatalar, Ultrason. Sonochem.
012, 19, 1108.
−
1
cm ): 3089, 3058, 3033, 1743, 1575, 1563, 1466, 1444,
265, 1022, 801, 743, 690; H NMR (400 MHz, CDCl ):
3
1
1
2
δ = 6.89 (m, 1H), 7.28 (m, 1H), 7.32 (m, 2H), 7.37 (m,
H), 7.45 (m, 1H), 7.96 (m, 2H), 8.56 (m, 1H).
[
[
[
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24] S. Askari, R. Halladj, Ultrason. Sonochem. 2012, 19, 554.
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ORCID
27] V. Kandathil, T. S. Koley, K. Manjunatha, R. B. Dateer, R. S.
Keri, B. S. Sasidhar, S. A. Patil, S. A. Patil, Inorg. Chim. Acta
Azadeh Tadjarodi http://orcid.org/0000-0003-0496-2322
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How to cite this article: Tadjarodi A, Dehghani
M, Imani M. Green synthesis and characterization
of palladium nanoparticles supported on zeolite Y
by sonochemical method, powerful and efficient
catalyst for Suzuki‐Miyaura coupling of aryl halides
with phenylboronic acid. Appl Organometal Chem.
1
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Appl Organometal Chem. 2017, 31, 1.
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Polym. 2017, 116, 9.
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