Journey on Greener Pathways via Synthesis of Pd/KB Polymeric Nanocomposite as a Recoverable Catalyst for the Ligand-Free Oxidative Hydroxylation of Phenylboronic Acid and Suzuki–Miyaura Coupling Reaction in Green Solvents

Article abstract of DOI:10.1007/s10562-018-2583-1

This paper reports a new and straightforward technique for the preparation of catalytically active palladium nanoparticle (Pd NPs) supported on the polymer surface derived from virgin polythene (Kaldnes Bio media filter) (Pd/KB nanocomposite). The morphology, structure and composition of Pd/KB nanocomposite were characterized by SEM, TEM, XRD, EDX and UV–Vis spectroscopy. The as-prepared catalyst presented excellent catalytic activity for the ligand-free oxidative hydroxylation of phenylboronic acid and Suzuki–Miyaura coupling reaction in water and ethanol as green solvents. In addition, the catalyst could be easily separated from the reaction mixture and reused four times with no loss of activity. The advantages of this eco-friendly protocol are using the cheap, clean, and nontoxic precursors, simple reaction setup, high yield of products and elimination of ligand and homogeneous catalysts. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-018-2583-1

Catalysis Letters
https://doi.org/10.1007/s10562-018-2583-1
Journey on Greener Pathways via Synthesis of Pd/KB Polymeric
Nanocomposite as a Recoverable Catalyst for the Ligand-Free
Oxidative Hydroxylation of Phenylboronic Acid and Suzuki–Miyaura
Coupling Reaction in Green Solvents
Bahareh Feizi Mohazzab1 · Babak Jaleh1 · Mahmoud Nasrollahzadeh2 · Zahra Issaabadi2
Received: 8 July 2018 / Accepted: 29 September 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
This paper reports a new and straightforward technique for the preparation of catalytically active palladium nanoparticle (Pd
NPs) supported on the polymer surface derived from virgin polythene (Kaldnes Bio media filter) (Pd/KB nanocomposite).
The morphology, structure and composition of Pd/KB nanocomposite were characterized by SEM, TEM, XRD, EDX and
UV–Vis spectroscopy. The as-prepared catalyst presented excellent catalytic activity for the ligand-free oxidative hydroxy-
lation of phenylboronic acid and Suzuki–Miyaura coupling reaction in water and ethanol as green solvents. In addition, the
catalyst could be easily separated from the reaction mixture and reused four times with no loss of activity. The advantages of
this eco-friendly protocol are using the cheap, clean, and nontoxic precursors, simple reaction setup, high yield of products
and elimination of ligand and homogeneous catalysts.
Graphical Abstract
OH
B(OH)2
H2O2, r.t.
Dried in 60oC
for 2 h
Sonicated in
distilled water
Pd/KB nanocomposite
Sttirring for 24 h in
homogeneous Pd NPs solution
K2CO3, H2O:EtOH, 90 o
C
(HO)2B
+
R
I
R
Keywords Pd/KB nanocomposite · Kaldnes Bio media filter · Recoverable catalyst · Hydroxylation · Suzuki–Miyaura
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

B. Feizi Mohazzab et al.
acid under heterogeneous conditions has been a main chal-
lenge in organic synthesis.
1 Introduction
With regard to the development of heterogeneous cata-
lysts [38–40], Pd/KB nanocomposite was prepared via an
easy, new, and low-cost process using Kaldnes Bio media
filter as stabilizing agent. The Pd/KB nanocomposite
was characterized by various techniques and used for the
ligand-free oxidative hydroxylation of phenylboronic acid
and Suzuki–Miyaura coupling reaction. To the best of our
knowledge, there has been yet no example of Kaldnes Bio
media filter for the synthesis of metal nanocatalysts and its
application in the catalytic reactions.
Recently, metal nanoparticles (MNPs) have potential
applications especially in biotechnology, materials science
and modern chemistry [1–4]. Particularly for the fabri-
cation of catalysis, various polymers are very attractive
materials for the MNPs stabilization due to their multiple
possible interactions with combined properties from the
polymer framework and the metal cluster [5]. Many scien-
tists have been used various polymers such as chitosan [6],
starch [7] and carboxymethyl cellulose [8] for the synthe-
sis of the metal nanocatalysts. Among the polymers, the
Kaldnes Bio media filter is composed of virgin polythene.
In addition, these polymeric materials modified with the
promoted additions of bioenzyme and improves the enzy-
matic catalysis, so that Kaldnes Bio media filter shows a
good and larger specific surface.
2 Experimental
2.1 Instruments and Reagents
During the past decades, Pd-catalyzed coupling reactions,
such as Heck, Suzuki, Sonogashira and Buchwald [9, 10]
as well as other reactions, have contributed greatly to the
powerful and straightforward fabrication of carbon–carbon
bonds, which have profound impact and applications in
medicine, cosmetics, pharmacology and synthesis of poly-
mers, ligands and advanced materials [11–13]. There are
various methods for the preparation of biaryl compounds in
Suzuki C–C coupling reactions by using different homog-
enous or heterogeneous catalysts [14, 15]. Although a num-
ber of homogeneous Pd catalysts have been used for Suzuki
coupling reactions but these catalyst systems suffered from
drawbacks such as tedious work-ups, high operational costs,
short life time, and the difficulty of separating from the reac-
tion mixture. Therefore, synthesis of heterogeneous catalysts
by suitable supports such as CuO [16], GO [17], TiO2 [2],
Fe3O4 [3] and various solid materials [18–34] are very desir-
able for overcome this problem. For example, Baran research
group published several reports for Suzuki C–C coupling
reactions using various solid materials such as chitosan, cel-
lulose, starch and bio-macromolecule Schiff based supported
homogenous or heterogeneous palladium catalysts or pal-
ladium nanoparticles [18–34].
High-purity chemical reagents were purchased from the
Merck KGaA, Sigma–Aldrich company and were used
without further purification. Polymer substrate was pur-
chased from Tianda chemical Industrial (Kaldnes bio
media filter, PE03, density= 155 kg m−3, specific surface
area > 834 m2 m−3, material = virgin polythene). Exist-
ence Pd NPs in solution (before and after deposition) was
monitored with a UV–Vis spectrophotometer (PG instru-
ments Ltd, T80). The size of the Pd NPs was visualized
using Transmission Electron Microscopy (TEM, Zeiss-
EM10C-100 kV). Sample structures were evaluated using
X-ray diffraction (XRD, Unisantis xmd300). The X-ray
wavelength is 0.154 nm and diffraction patterns were
recorded over the 2θ range 10°–80°. Morphology of samples
were assessed by scanning electron microscope (SEM, Cam
scan MV2300), also the energy-dispersive X-ray spectrom-
etry (EDX) was used for qualitative elemental analysis of the
samples before and after deposition. To illuminate the depo-
sition of Pd NPs elemental mapping of sample was done.
In addition, the thermogravimetric analysis (TGA, linseis
STA PT-1000) of Pd/KB nanocomposite was investigated.
The elemental contents of palladium in the Pd/KB nano-
composite were determined by inductively coupled plasma
atomic emission spectroscopy (ICP-AES) using Thermo
electron corporation make, (IRIS Intrepid 11 XDL instru-
ment). Change of the chemical composition on the polymer
surface were preformed by the attenuated total reflection
technique (FT-IR-ATR, Bruker, Alpha).
Nowadays, organic synthesis of phenols attracts consid-
erable attention due to its applications in the preparation
of the oxygen-containing heterocycles, polymer chemistry,
pharmaceuticals and chemical industries. Recently, several
efficient and straight procedures have been established to
convert arylboronic acids into phenols. Among the various
catalytic procedures reported for the direct hydroxylation
of phenylboronic acid [35–37] only a few heterogeneous
catalysts have been explained, including Amberlite-IR-120
resin and clay-entrapped Cu(OH)x. Therefore, the devel-
opment of a highly efficient and environmentally benign
approach for the oxidative hydroxylation of phenylboronic
2.2 Preparation of the Pd NPs
Pd NPs were synthesized according the procedure reported
by our pervious work [41]. The concentration of the Pd
NPs colloid was 7 × 10−3 mol L−1. A well homogeneous
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Journey on Greener Pathways via Synthesis of Pd/KB Polymeric Nanocomposite as a Recoverable…
solution was prepared using ultrasonication (20 min) at
room temperature.
2.5 Preparation of Phenol via Oxidative
Hydroxylation of Phenylboronic Acid
In a typical procedure, the Pd/KB nanocomposite (4.0 mg)
was added to 1.0 m mol of phenylboronic acid and 0.5 mL
H2O2 (30% aq.) while the reaction mixture was stirred at
room temperature for 5 min. After completion of the reaction
(as monitored by TLC), the catalyst was separated and the
reaction mixture extracted with diethyl ether. The ethereal
phase was separated and evaporated to give the phenol as
pure product. The product was characterized by spectral data.
2.3 Pd NPs Deposition on Samples
At first, samples were ultrasonically washed using distilled
water and dried at 60 °C in an oven for 2 h. Then 10 sam-
ples of polymer substrate (1.6128 g) were floated in 20 mL
of the Pd NPs colloid solution. The solution was stirred
for 24 h. After stirring samples were separated and dried
at 60 °C in an oven for 2 h, Fig. 1. To assure of Pd NPs
deposition on samples we recorded solution’s discolora-
tion. The Pd NPs colloid exhibit significant differences in
color (visible to bare eye). Before stirring, the solution
was dark brown which after 24 h its color turns to gold
demonstrated the deposition of Pd NPs on the surface of
samples. the pristine samples and deposited samples are
shown as S1 and S2, respectively.
3 Results and Discussion
3.1 Characterization of Catalyst
In order to confirm deposition of the Pd NPs on the surface
of samples, UV–Visible spectral analysis was acquired for
the solutions, the results were shown in Fig. 2, which declare
color variance between the solutions. Figure 2a displays the
absorption spectra of the Pd NPs colloid, some indication
of the absorption band can be seen around 257 nm that is
owing to the incitement of surface Plasmon vibrations of the
Pd NPs [41, 42]. The image of the reaction shows the change
in solution color (from dark brown to yellow). A decrease in
the background of spectrum (b) indicates deposition of the
Pd NPs on the surface of the samples.
2.4 Preparation of Biaryls via Suzuki Coupling
Reaction
In a typical reaction, a mixture of 1.0 mmol of aryl hal-
ide, 1.1 mmol of phenylboronic acid, 2.0 m mol of K2CO3,
8 mL of a 1:1 mixture EtOH:water and 0.05 g of the Pd/
KB nanocomposite was stirred at 90 °C for the appropri-
ate time. After completion of the reaction (as monitored by
TLC), the reaction mixture was cooled to room temperature
and the catalyst was filtered out. After removal of solvent,
the residue was then purified by flash chromatography on
silica gel to give the desired coupling product. The product
was characterized by melting point and spectral data. The
obtained structure was confirmed by NMR spectroscopy.
TEM analysis was used to clear display of the shape and
the size of the nanoparticles. To determine the size and the
shape of the Pd NPs, TEM method was used. The average
particle diameter of the Pd NPs was estimated by Image J
software with measuring the diameter over 100 NPs. Fig-
ure 3 presents the TEM image of the Pd NPs and diam-
eter’s distribution. Figure 3a declares that Pd NPs are almost
Fig. 1 Schematic drawing of
deposition Pd NPs on samples
Sonicated in
distilled water
60oC
h
Dried in
2
for
Sttirring for 24 h in
homogeneous Pd NPs solution
1 3

B. Feizi Mohazzab et al.
Fig. 2 UV–Visible spectra of
the Pd NPs colloid a before and
b after deposition for 24 h
Fig. 3 TEM image of the Pd NPs, the dark regions on the background present Pd NPs (a), Histogram showing the distribution of diameters
obtained from ImageJ software (b)
spherical with the average diameters of about 5 nm. Also
the Pd NPs’ diameter distribution in Fig. 3b, shows a sort of
symmetrical Gaussian distribution function.
plane of the Pd (JCPDS 46-1043) [44], as shown in Fig. 4b.
This peak shows that Pd NPs were decorated on HDPE in
dominate (111) plane.
The structures of S1 and S2 were considered by XRD. Fig-
ure 4 shows XRD patterns of S1 and S2, it can be seen that
the characteristic diffraction peak of these samples exhibits a
strong peak at 21.6°, also a less intensive peak at 24.0° due to
the typical orthorhombic unit cell structure of (110) and (200)
reflection planes from HDPE (JCPDS 53-1859) [43], respec-
tively. On top of that the XRD pattern of S2 shows a reflection
peak at 49.119° derived from the ordered arrangement of (111)
Bragg’s law [45] can estimate the lattice parameter of a
particular cubic system through the following relation:
ꢀ
dhkl
=
(1)
(2)
2sinꢁ
a
dhkl
=
√
h2 + k2 + l2
1 3

Journey on Greener Pathways via Synthesis of Pd/KB Polymeric Nanocomposite as a Recoverable…
Fig. 5 SEM micrograph of the fracture surface of virgin specimen
with different magnification
tabulated atomic and weight ratios. Comparison of Fig. 7a,
b revealed that Pd NPS are deposited on the surface of
samples which is agreed with XRD and SEM analyses.
The EDX mapping analysis Fig. 8 demonstrated the Pd
NPs were random distributed on S2 surface.
Fig. 4 XRD patterns of a virgin sample and b deposited sample
where a is the lattice parameter of the cubic crystal, h, k,
and l are the Miller indices of the Bragg plane, the variable
dhkl is the distance between atomic layers in a crystal and λ
is the wavelength of the X-ray radiation used. Pd has face
center cubic structure, by using Eq. (1, 2) and λ=0.154 nm,
Pd lattice parameter was calculated 3.89 Å due to strongest
reflection of (111) plane.
Morphology of pure and deposited sample was studied
by using Scanning electron microscopy (SEM) equipped
with EDX detector. SEM images of fracture surface of S1
and S2 with different magnification are observed in Figs. 5
and 6, respectively. Figure 5 a–d clearly shows a typical
ocean-like, porosity surface and lamellar structure of the
S1. This porosity provides a good space for deposition. As
we can see in Fig. 6, the Pd NPs wasn’t uniformly depos-
ited on the surface of the samples. Also, the comparison
Figs. 5b and 6b clearly shows that the surface became
slightly smoother for influence of Pd NPs on the surface.
The elemental composition of S1 and S2 was studied
by EDX analysis; the results were reported in Fig. 7 with
Fig. 6 Surface morphologies of deposited sample, the dark gray sur-
face display HDPE and white part show Pd NPs deposited on surface
1 3

B. Feizi Mohazzab et al.
Fig. 9 Thermogravimetric curve of pure sample (s1) and deposited
sample (s2)
Table 1 Mass-loss temprature obtained from TGA thermogram of
samples
Sample name
Mass loss temperature ( 2 °C)
T10
T50
T90
Fig. 7 EDX analysis of a virgin sample, b deposited sample with
Pure sample
Pd/KB nancomposite
398
376
452
443
476
472
ratio of elemental
The T10, T50 and T90 represent temperature of onset degradation, 50%
mass-loss and 90% mass-loss, respectively
To assess the thermal stability of polymeric nanocom-
posites, TGA analysis was used. Figure 9 shows the mass-
loss behavior as a function of temperature for the samples,
before and after its deposition. Through the curves both
samples display similar thermograms with a single mass-
loss zone centered around 180 °C. The Pd NPs affect the
thermal stability of the pure samples negatively as the
curves shown. We have to consider that deposition of Pd
NPs on pure samples shifts the TGA curves to lower tem-
peratures but it isn’t significantly which is probably related
to the thermal conductivity of Pd NPs.
results under nitrogen gas at ramp rate of 10 °C are given
in Table 1. The results suggest that the diversity of tempra-
tures in samples decrease by increasing the temprature, it
is probably due to the fact that Pd NPs deposited on poly-
mer’s surface by which the degradation occours on the sur-
face of the samples. As a result, in high tempratures, the
diversity of tempratures between samples decline because
at this range the bulk of samples are degrading so the sam-
ples have the same respond. As manufacturer has anounced
there is some points that are important to understand
influence of Pd NPs depositon on polymer substrate. The
Fig. 8 Mapping of deposited
sample, the purple dot and
gray dot show distribution of
Carbon and Pd on the surface,
respectively
1 3

Journey on Greener Pathways via Synthesis of Pd/KB Polymeric Nanocomposite as a Recoverable…
3.2 Investigation of the Catalytic Activity of the Pd/
KB Nanocomposite
The catalytic activity of the Pd/KB nanocomposite towards
the ligand-free oxidative hydroxylation of phenylboronic acid
and Suzuki–Miyaura coupling reaction has been investigated.
3.2.1 Investigation of the Catalytic Activity of the Pd/
KB Nanocomposite Through the Suzuki–Miyaura
Coupling Reaction
For optimization of the reaction conditions, we initially
selected iodobenzene and phenylboronic acid as a model
reaction. The reaction was performed successfully in the
presence of 0.05 g of the Pd/KB nanocomposite as palla-
dium source and 2.0 m mol of K2CO3 as an efficient base.
As expected, no target product could be detected in the
absence of the Pd/KB nanocomposite. The reaction was
also carried out in the presence of different amount of the
Pd/KB nanocomposite as catalyst which the results are sum-
marized in Table 2. In addition, the effects of the several
bases (Na2CO3, K2CO3, Et3N) and solvents (H2O, EtOH,
mixture H2O:EtOH) were examined. Among the tested
bases and solvents, K2CO3 and mixture H2O:EtOH were
found to be superior for the highest yield of product. The
best result was obtained with phenylboronic acid (1.1 m
mol), iodobenzene (1.0 m mol), Pd/KB nanocomposite
(0.05 g), K2CO3 (2.0 m mol), and mixture H2O/EtOH (1:1)
at 90 °C for 90 min, which obtained the product in a high
yield (96%). Larger amounts of catalyst did not lead to a
significant change in the yield and time (Table 2, entry 6).
Fig. 10 FT-IR spectra of the pure sample, Pd/KB nanocomposite and
recycled Pd/KB nanocomposite
the applicable temperature for Kaldnes bio media filter is
in range of 5–60 °C; both sample have the same action at
100 °C.
Metal content in Pd/KB nanocomposite analyzed by ICP-
AES shows the presence of 3.7% (w/w) of palladium.
FT-IR spectra of the pure sample (KB), Pd/KB nano-
composite and recycled Pd/KB nanocomposite are shown
in Fig. 10. The FT-IR analysis of KB and Pd/KB nanocom-
posite confirm that there was no change in functional groups
after the immobilization of Pd NPs on KB.
Table 2 Optimization conditions for the Suzuki coupling reaction by using Pd/KB nanocomposite
Pd/KB
Base,
nanocomposite
solvent,
+
I
B
(HO)2
90 oC
Entry
Solvent
Pd/KB (g)
Base
Time (min)
Yield (%)a
1
2
3
4
5
6
7
8
EtOH
H2O
0.05
0.05
0.05
0.05
0.05
0.07
0.03
0.05
K2CO3
K2CO3
K2CO3
Na2CO3
Et3N
K2CO3
K2CO3
–
150
180
90
180
150
90
70
50
96
65
70
96
72
Trace
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
EtOH/H2O
100
120
Reaction conditions: Iodobenzene (1.0 m mol); phenylboronic acid (1.1 m mol); K2CO3 (2.0 m mol); EtOH:H2O (1:1, 8.0 mL), 90 °C
aIsolated yield
1 3

B. Feizi Mohazzab et al.
Table 3 Effect of the Pd/KB nanocomposite on the Suzuki coupling reaction of different aryl halides with phenylboronic acida
Pd/KB
nanocomposite
2O:EtOH,
X
+
B(OH)2
K
H
CO
90 oC
,
3
2
R
R
Entry
R
X
Time (min)
Yield (%)a
1
2
3
4
5
6
7
8
H
I
I
I
I
I
I
Br
Br
Br
Br
Br
Br
90
90
90
90
90
96
94
93
92
95
84
94
86
91
87
82
80
4-Me
4-OMe
2-OMe
4-COMe
3-NO2
H
4-Me
4-OMe
4-COMe
4-Cl
90
150
150
150
150
150
150
9
10
11
12
3-NO2
Reaction conditions: aryl halide (1.0 m mol), phenylboronic acid (1.1 m mol), Pd/KB nanocomposite (0.05 g), K2CO3 (2.0 m mol), EtOH:H2O
(1:1, 8.0 mL) at 90 °C
aIsolated yield
Further, the scope of the Pd/KB nanocomposite was stud-
ied with various aryl halides (Table 3). The corresponding
biaryls were obtained in good to excellent yields using dif-
ferent aryl halides possessing both electron-releasing and
electron-withdrawing groups. All the products are known
and the melting points were consistent with those reported
in the literature [18–34, 46–60].
Table 4 Reaction conditions for the oxidative hydroxylation of phe-
nylboronic acid under ligand- and solvent-free conditions
OH
B(OH)2
Pd/KB
nanocomposite
r.t.
H
O
,
2
2
3.2.2 Investigation of the Catalytic Activity of the Pd/KB
Nanocomposite Through Oxidative Hydroxylation
of Phenylboronic Acid
Entry
Pd/KB nanocompos- Time (min)
ite (mg)
Yield (%)a
1
2
3
4
5
–
–
4.0
7.0
2.0
60
30 h
5
5
70b
95
95
78
In this part, we disclose our work on the Pd/KB nanocom-
posite catalyzed oxidative hydroxylation of phenylboronic
acid. Our initial investigation was performed with phenylbo-
ronic acid by using 30% aq. H2O2 at room temperature as
a model system. Trace amounts of the phenol product were
observed in the absence of the Pd/KB nanocomposite as a
catalyst (Table 4, entry 1). A decrease in the Pd/KB nano-
composite loading from 4.0 to 2.0 mg afforded the product
in lower yield. No significant improvement on the yield was
observed using higher amounts of the catalyst. The best
result was obtained with 4.0 mg of the Pd/KB nanocompos-
ite and 0.5 mL of 30% aq. H2O2 (Table 4, entry 3).
5
13
Reaction conditions: phenylboronic acid (1.0 m mol), H2O2 (30% aq.,
0.5 mL); room temperature
aIsolated yield
bThe reaction did not reach to completion
Kaldnes Bio media filter (Table 5). However, the synthe-
sized catalysts by Baran research group could be carried
out Suzuki–Miyaura coupling reaction in shorter times and
higher yields under microwave or ultrasound irradiation
(Table 5, entries 9–25). The present manner offers several
remarkable features, compared with the other literature
works on the oxidative hydroxylation of phenylboronic acid
and Suzuki–Miyaura coupling reaction such as:
Also, the catalytic performance of the Pd/KB nano-
composite in the oxidative hydroxylation of phenylboronic
acid at room temperature and Suzuki–Miyaura coupling
reaction under thermal conditions is compared with other
reported catalysts in the literature [18–34, 46–60] and better
activity is obtained by the synthesized nanocatalyst using
1 3

Journey on Greener Pathways via Synthesis of Pd/KB Polymeric Nanocomposite as a Recoverable…
Table 5 The Pd/KB nanocomposite catalyzed the oxidative hydroxylation of phenylboronic acid and Suzuki–Miyaura coupling reaction com-
pared to reported methods
Entry
Reaction conditions
Temp. (°C)
Time
Yield (%)a
Refs.
Oxidative hydroxylation of phenylboronic acid to phenol
1
2
3
4
5
6
7
8
CuSO4, 1,10-phenanthroline, KOH, H2O
CuSO4·5H2O, ellagic acid, MeOH, air
PhI, NaIO4, MeCN:H2O
rt
3 h
8 h
8 h
15 min
1 h
28 h
5 min
5 min
90
91
67
92
98b
81
94
95
[46]
[47]
[48]
[49]
[50]
[51]
[52]
This work
60
80
rt
40
rt
Ag NP mont K-10, H2O2
PdCl2(PPh3)2, KF, tBuOH/H2O, CO/O2 (3:1), 1 atm
[Ru(bpy)3Cl2]·6H2O, iPr2NEt, DMF, visible light irradiation, air
Pd/bentonite nanocomposite
rt
rt
Pd/KB nanocomposite
Suzuki–Miyaura coupling reaction between 4-bromoanisole with phenylboronic acid
9
Chitosan-pyridil-based Pd(II)
Robust starch-based Pd(II)catalyst (ST-Shf-Pd)
Pd@chitosan/starch nanocomposite
Chitosan-Ulva supported Pd(II)
Magnetically separable sporopollenin-based Pd(II)
OCMCS-3aPd
50, MW
50, MW
50, MW
50, MW
50, MW
100
60, US
50, MW
50, MW
50, MW
50, MW
50, MW
MW, 350 W
50, MW
50, MW
50, MW
MW, 400 W
100
5 min
0.1 h
0.1 h
4 min
0.08 h
48 h
30 min
0.1 h
4 min
6 min
5 min
0.08 h
5 min
4 min
5 min
0.08 h
7 min
12 h
9 h
6 h
12 h
24 h
5 h
12 h
12 h
150 min
>99
99
98
99
99
97
94
99
99
97
99
98
96
>99
97
100
94
86
68
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
This work
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
Pd NPs@CMC/AG
Cellulose Schiff base supported Pd(II)
Biopolymer (chitosan)-based pincer-type Pd(II)
AG-Pd
Chitosan/cellulose-Pd(II)
Pd nanocatalyst on chitosan/cellulose composite
Pd nanocatalyst on agar/pectin composite
Pd/OCMCS-SBL
Chitosan Schiff base supported Pd(II)
Starch supported Pd(II)
CL-Gly-Pd
Pd-1/FSG
pEVPBr-Pd
Pd(OAc)2, polymer-supported ferrocenylphosphine
PS-PEG600-NHC-Pd
Pd-PVP
Agarose hydrogel supported Pd nanoparticles
Polymer-supported Pd-NHC complex
Fe3O4-Pd
90
110
50
90
80–100
50
50
67
76
89
80
68.5
90
91
Pd/KB nanocomposite
90
aIsolated yields
bGC yields
Table 6 Reusability of the Pd/KB nanocomposite for Suzuki–Miyaura coupling reaction between iodobenzene with phenylboronic acid
Pd/KB
nanocomposite
2O:EtOH,
I
+
B(OH)2
CO
90 oC
K
H
,
3
2
Run
1
2
3
4
5
Yield (%)a
96
96
95
94
93
Reaction conditions: Iodobenzene (1.0 m mol), phenylboronic acid (1.1 m mol), Pd/KB nanocomposite (0.05 g), K2CO3 (2.0 m mol), EtOH:H2O
(1:1, 8.0 mL) at 90 °C
aIsolated yield
1 3

B. Feizi Mohazzab et al.
in functional groups and morphological characteristics of
the Pd/KB nanocomposite.
B(OH)2
Yield %
95 %
Run
First
First
Recycle
4 Conclusions
95 %
95 %
Second
Recycle
Pd/KB
This study has developed a straightforward and efficient
protocol for the synthesis of the immobilized Pd NPs on the
Kaldnes Bio media filter surface (Pd/KB nanocomposite).
The catalyst exhibited high catalytic activities in ligand-
free oxidative hydroxylation of phenylboronic acid and
Suzuki–Miyaura coupling reaction. The advantages of this
safe protocol include a simple reaction setup, elimination
of ligand and homogeneous catalysts and easy work-up and
high yields. The Pd/KB nanocomposite was characterized
by SEM, TEM, XRD, EDX and UV–Vis spectroscopy. The
catalyst could be readily recovered and reused for four cycles
with no loss of activity.
nanocomposite
Third
Recycle
r.t.
,
2
H
O
95 %
94 %
94 %
2
Fourth
Recycle
Recycle
OH
Fifth
Fig. 11 Reusability of the Pd/KB nanocomposite for the oxidative
hydroxylation of phenylboronic acid to phenol
•
Green synthesis of the Pd/KB nanocomposite in water
without using any dangerous reducing agents.
Toxic ligands or homogeneous catalysts are not needed.
Ease of handling and cost efficiency of the Kaldnes Bio
media filter.
Acknowledgements We gratefully acknowledge from the Iranian Nano
Council, Bu-Ali Sina University and University of Qom for the support
of this work.
•
•
•
The use of Kaldnes Bio media filter as an economic and
effective alternative.
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•
•
Wide scope of substrates with high yields.
The use of green solvents in the oxidative hydroxyla-
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Affiliations
Bahareh Feizi Mohazzab1 · Babak Jaleh1 · Mahmoud Nasrollahzadeh2 · Zahra Issaabadi2
2
* Mahmoud Nasrollahzadeh
Department of Chemistry, Faculty of Science, University
of Qom, Qom 3716146611, Iran
mahmoudnasr81@gmail.com
1
Department of Physics, Faculty of Science, Bu-Ali Sina
University, Postal Code 65174, Hamedan, Iran
1 3