Palladium nanoparticle supported on nitrogen-doped porous carbon: Investigation of structural properties and catalytic activity on Suzuki–Miyaura reactions

Article abstract of DOI:10.1002/aoc.6403

Novel palladium-doped nanoporous carbon composite material obtained via thermolysis of amorphous zeolitic imidazolate framework (aZIF) was synthesized and used as an efficient catalyst on Suzuki–Miyaura cross-coupling reactions of aryl bromides. With this developed catalytic system, the Suzuki–Miyaura cross-coupling reaction was accomplished in aqueous solutions, and biaryls were obtained in good to excellent yields in a short reaction time. The APC-750@Pd catalyst was characterized by Fourier Transform Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Scanning Electron Eicroscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM), Thermal Gravimetric Analysis (TGA), Differential Thermal Analysis (DTA), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Brunauer–Emmett–Teller (BET) analysis tecniques. N-doped porous carbon material (NPC-1000) was synthesized by thermolysis from aZIF. Activated porous carbon material (APC-750) was fabricated via fused at 750°C with KOH from NPC-1000. The APC-750@Pd was obtained as a result of the interaction of APC-750 and PdCl₂ in deionized water. The cross-coupling reaction of different aryl bromides with phenylboronic acid was investigated to show the potential of the APC-750@Pd in the Suzuki–Miyaura cross-coupling reactions. The APC-750@Pd catalyst could be recycled at least five times with a 15% loss of catalytic efficiency in this catalytic system.

Full text of DOI:10.1002/aoc.6403

Received: 10 May 2021
DOI: 10.1002/aoc.6403
Revised: 14 July 2021
Accepted: 26 July 2021
R E S E A R C H A R T I C L E
Palladium nanoparticle supported on nitrogen-doped
porous carbon: Investigation of structural properties and
catalytic activity on Suzuki–Miyaura reactions
Nesrin Bu gꢀ day1
2
1
| Serdar Altın
| Sedat Ya s¸ ar
1
Faculty of Science and Art, Department
Abstract
_
of Chemistry, Inönü University, Malatya,
Turkey
Novel palladium-doped nanoporous carbon composite material obtained via
thermolysis of amorphous zeolitic imidazolate framework (aZIF) was
synthesized and used as an efficient catalyst on Suzuki–Miyaura cross-
coupling reactions of aryl bromides. With this developed catalytic system, the
Suzuki–Miyaura cross-coupling reaction was accomplished in aqueous
solutions, and biaryls were obtained in good to excellent yields in a short reac-
tion time. The APC-750@Pd catalyst was characterized by Fourier Transform
Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Scanning Electron
Eicroscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Transmission
Electron Microscopy (TEM), Thermal Gravimetric Analysis (TGA), Differential
Thermal Analysis (DTA), Inductively Coupled Plasma Mass Spectrometry
2
Faculty of Science and Art, Department
_
of Physics, Inönü University, Malatya,
Turkey
Correspondence
Sedat Ya s¸ ar, Faculty of Science and Art,
_
Department of Chemistry, Inönü
University, Malatya 44280, Turkey.
Email: sedat.yasar@inonu.edu.tr
Funding information
_
Inönü University Research Council
(ICP-MS) and Brunauer–Emmett–Teller (BET) analysis tecniques. N-doped
porous carbon material (NPC-1000) was synthesized by thermolysis from aZIF.
ꢀ
Activated porous carbon material (APC-750) was fabricated via fused at 750 C
with KOH from NPC-1000. The APC-750@Pd was obtained as a result of the
interaction of APC-750 and PdCl in deionized water. The cross-coupling
2
reaction of different aryl bromides with phenylboronic acid was investigated to
show the potential of the APC-750@Pd in the Suzuki–Miyaura cross-coupling
reactions. The APC-750@Pd catalyst could be recycled at least five times with
a 15% loss of catalytic efficiency in this catalytic system.
K E Y W O R D S
amorphous ZIF, C–C bond formation, cross-coupling, MOF, Suzuki–Miyaura
1
| INTRODUCTION
nonreusability, and separation problem of product or cat-
[
8–13]
alyst from reaction media.
The problems mentioned
The Suzuki–Miyaura reaction of aryl halides with phe-
nylboronic acid derivatives in the presence of a palladium
catalyst is a critical topic in the synthesis of biaryls. These
biaryls are commonly used in various fields, such as med-
above have been solved using heterogeneous palladium
[
14–18]
catalysts.
Sajiki and coworkers were the first to use
[19]
Pd/C for ligand-free Suzuki–Miyaura reactions.
lowing that, some researchers extended the use of Pd/C
Fol-
[1–7]
[20–23]
icine, cosmetics, and engineering materials.
Despite
in various reactions.
Pd nanoparticles (NPs) have
intensive studies, homogeneous palladium catalysts for
coupling reactions are suffered from stability,
been studied on a variety of supports (silica, zeolite,
organic polymers, and carbon) to improve their catalytic
Appl Organomet Chem. 2021;e6403.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
1 of 15
https://doi.org/10.1002/aoc.6403

2
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BUĞDAY ET AL.
activity and recyclability in recent years. 23–25] Despite
this, the catalytic performance is still insufficient because
Pd NPs are sensitive to leaching and accumulation,
resulting in catalytic activity degradation in some situa-
tions. As a result, developing suitable supports for Pd
NPs catalysts for effective heterogeneous catalysis with
high recyclability is critical, both economically and envi-
ronmentally. Thus, developing a Pd@C catalyst is still a
challenge and promising heterogeneous commercial
catalyst.
[
The porous materials such as zeolites, porous metal,
porous glass, porous ceramics, and nanoporous carbon
(NPC) have gained importance due to their intrinsic
properties and have suitable properties for broad applica-
[
44–47]
tions.
Recently, nitrogen-doped NPCs have atrached
considerable attention. Generally, NPCs have conven-
tionally been synthesized by in situ approaches and post-
treatment approaches such as chemical vapor deposition,
ball milling, bottom-up synthesis, wet chemical methods,
thermal annealing of carbon templates with heteroatom
[48]
Metal–organic frameworks (MOFs) have emerged as
auspicious functional materials for gas storage, separa-
tion, heterogeneous catalysis, sensing, drug delivery, and
due to their high
degree of customizability in the properties
precursors, plasma, and arc-discharge approaches.
Under favorable thermolysis conditions, MOFs, aMOFs,
ZIFs, and aZIFs may be attractive candidates for produc-
[26–36]
electrochemical applications
ing highly porous nitrogen-doped carbon materials as
[37]
[49]
and their
templates or precursors.
Several MOFs and ZIFs have
superior features such as high surface area, large pore
size, high porosity, chemical tunability, and thermal sta-
bility. Amorphous MOFs (aMOFs) are MOFs with an
irregular network formed by inorganic metal nodes and
been demonstrated as promising templates to construct
[
49–53]
NPCs.
NPC materials synthesized from ZIFs have
long been the most important and conventional support
for heterogeneous catalysts due to their large pore vol-
[38]
organic linkers as in MOFs
and do not have any long-
This haphazard arrange-
ume and high specific surface area, as well as their excel-
[39,40]
[54–58]
distance periodic order.
lent thermal, chemical, and mechanical stability.
It
ment of the atoms in aMOFs leads to form broad peaks in
X-ray diffraction (XRD) patterns instead of Bragg peaks.
Zeolitic imidazolate frameworks (ZIFs), a thermally and
chemically stable subclass of MOFs, have the same topol-
ogy as zeolites and one of the promising classes of emerg-
has been demonstrated that incorporating nitrogen into
carbon materials will improve the mechanical properties
and durability of noble metal NPs (e.g., Pt and Pd), which
[
59,60]
is crucial for heterogeneous catalysis.
In addition, the introduction of electron-donating N
species improves the charge density distribution and
boosts the carbon skeleton activity, endowing the carbon
framework with enhanced wettability and good affinity
to aqueous solutions. In order to develop the catalyst
with the superior properties mentioned above on the
[41]
ing materials.
ZIFs and amorphous ZIFs (a-ZIFs) have
properties similar to silica networks that led to higher
thermal and chemical stability in organic and aqueous
media. ZIFs have been widely analyzed in the literature,
[42,43]
while a-ZIFs have received much less attention.
SCHEME 1 Schematic illustration of the synthesis of APC-750@Pd catalyst and its application on Suzuki–Miyaura reaction

BUĞDAY ET AL.
3 of 15
0
synthesized biaryls under suitable conditions, herein, Pd-
doped NPC (APC-750@Pd) was produced from aZIF by
carbonization and activation with KOH. Pd NP was
immobilized onto the N-doped APC-750. The Suzuki–
Miyaura coupling reactions of aryl bromides and phe-
nylboronic acids were investigated to show the efficiency
of the APC-750@Pd catalyst of Scheme 1.
750@Pd solid was obtained after centrifugation, and the
black solid was washed a couple of times with DI and
ꢀ
dried at 60 C for 24 h. As a result of the analysis with
inductively coupled plasma mass spectrometry (ICP-MS),
it was found that there is 1.068% Pd in APC-750@Pd.
2.2 | Characterization
2
2
2
| EXPERIMENTAL SECTION
.1 | Synthesis
The crystal structure analysis of the synthesized materials
was performed by an X-ray diffractometer labeled Rigaku
Rint 2000, which was powered by Cu Kα radiation for
0
characterization. The scan rate was chosen as 2 /min
ꢀ
ꢀ
.1.1 | Preparation of aZIF, NPCs, and Pd-
between 2 and 80 /min. The microstructural properties
and the surface morphology of the synthesized powders
were investigated by Leo EVO-40 VPX scanning electron
microscope (SEM). An Agilent 7800 ICP-MS was used to
determine the Pd amount in APC-750 @ Pd. XPS instru-
ment: Specs-Flex XPS, X rays: hn = 1486,6 eV monochro-
matic, spot 200 μm and energy resolution (hi-resolution
spectra): 0.8 eV were used. The Fourier transform infra-
red spectroscopy (FTIR) analyses of the synthesized pow-
doped activated porous carbon material (APC-
50@Pd)
7
In the synthesis of aZIF, 2-g zinc nitrate hexahydrate and
gr of 5,6-dimethylbenzimidazole were dissolved sepa-
2
rately in 20 mL of methanol. Then, these two solutions
were slowly mixed and stirred at room temperature for
2
h. White solids were formed after 2 min and collected
by centrifugation and then rinsed with a mixture of
methanol and deionized water (DI) for sufficient time.
Finally, the obtained white product was activated by sol-
vent exchange using ethanol and chloroform. Then white
solid powder was dried at room temperature and stored
under air condition. This white solid is labeled as aZIF.
The N-doped porous carbon material was obtained
via direct thermolysis of aZIF. First, a quartz boat con-
taining the white aZIF solid was placed into a high-
temperature tube furnace. Then, the furnace was heated
ders were determined by Perkin Elmer, which operated
À1
between 400 and 4000 cm
.
3 | RESULTS AND DISCUSSION
3.1 | Structural properties
The XRD patterns of aZIF, NPC-1000, APC-750, and
APC-750@Pd are shown in Figure 1, and three broad
peaks seen in XRD pattern analysis of aZIF may attrib-
uted to nanosized crystalline and/or amorphous type
ꢀ
to 1000 C for 2 h under an argon atmosphere using a
ꢀ
heating rate of 3 C/min. This black solid is labeled as N-
doped porous carbon materials (NPC-1000).
The as-synthesized porous carbon of NPC-1000 was
ꢀ
further activated by KOH at 750 C for 2 h under argon.
Firstly, NPC-1000 was mixed with KOH (w:w, 1:5), and
the mixture was placed in a tube furnace and then heated
ꢀ
to an activation temperature of 750 C for 1 h under an
argon atmosphere with a heating and cooling rate of
ꢀ
3
C/min. After that, the mixture was recovered and
washed three times with 1-M HCl and then washed with
ꢀ
sufficient DI. The obtained black solid was dried at 60 C
for 12 h. The black sample after activation was labeled as
APC-750. After the characterization of APC-750 by XRD,
PdCl (10 mg) and APC-750 (100 mg) were put into a
2
round bottom flask, and 15-mL DI was added refluxed
for 24 h. After cooled to room temperature, solid was cen-
ꢀ
trifuged and dried at 60 C for 12 h; 20-mg NaBH was
4
2
+
solved in a flask with 15-mL DI, and APC-750@Pd
was added to the flask. The pH of the solution was set to
0 by NH OH solution and refluxed for 2 h. The APC-
FIGURE 1 X-ray diffraction (XRD) patterns of amorphous
1
zeolitic imidazolate framework (aZIF), NPC-1000, and APC-750
4

4
of 15
BUĞDAY ET AL.
grain formation. According to the literature, we think
(TEM) to investigate the variation of their morphology.
The results are shown in Figure 3a–e.
[
38,61]
that the aZIF has amorphous type grain formation.
ꢀ
As shown in Figure 1, two broad peaks at 11.37 and
Figure 3a shows the surface morphology of aZIF,
which exhibits an irregular shape and porous structure
with the flake-type randomly oriented grain formations.
The flake-type grains have a grain size of no greater than
about 1 μm. The surface morphology of NPC-1000 and
APC-750 shows a similar irregular shape and porous
structure formation. Additionally, the flake-type grains
disappeared in both structures. The probable reasons
behind the disappearance of flake-type grains are carbon-
ization and fusing with KOH. The SEM images of APC-
750@Pd also confirm the morphology of the APC-750 is
not changed after the incorporation process of Pd species.
Figure 3d shows the elemental mapping analysis of APC-
750@Pd. As shown in this Figure 3e, the Pd atoms are
uniformly distributed and well dispersed. The TEM
images also show the presence of well-dispersed Pd NPs
on the APC-750. The ICM-MS analysis of APC-750@Pd
shows that it contains wt% of 1.068 Pd NPs
(0.049 mmol Pd).
ꢀ
1
6.31 for aZIF indicate short-range ordering in the struc-
ture and not repeated at 3D. The broad peaks at
ꢀ
ꢀ
ꢀ
2
θ = 11.24 and 22.22 for NPC-1000 and 2θ = 11.34
ꢀ
and 22.60 for APC-750 correspond to graphitize carbon
and carbon derivatives.
[
62]
The XRD pattern also shows
that the incorporation of Pd does not affect the structure
of APC-750 significantly. The XRD pattern of the
0
APC-750@Pd catalyst is shown significant peaks
ascribed to the Pd species at 2θ = 39.94, 46.64, and 67.94
correspond to the palladium NP planes (111), (200), and
(220), respectively. From these XRD results, the Pd-NPs
are produced successfully and well-dispersed on the acti-
vated porous carbon (APC-750).
Figure 2 shows the FTIR of aZIF, NPC-1000,
APC-750, and APC-750@Pd. It is seen that the bond
structure of aZIF is related to bonds of starting materials.
After heat treatment, several peaks were observed at
1
078.3, 1537.6, and 2935 for NPC-1000, which correspond
to C–C, C═C, and C–H stretching, respectively. After
The SEM images and elemental mapping of 5-times
reused APC-750@Pd are shown in Figure 4. The use of
the APC-750@Pd in the catalytic reaction causes small
changes in the morphology of the catalyst (Figure 4b).
The elemental mapping of the 5-times reused APC-
750@Pd catalyst shows the elements C, O, N, and
Pd. The ICM-MS analysis of 5-times reused APC-750@Pd
catalyst shows that it contains wt% of 0.96 Pd NPs (ꢁ10%
Pd leach from catalyst structure after five runs).
In order to clarify the porosity of the synthesized
materials, nitrogen adsorption–desorption was accom-
plished at 77 K, as shown in Figure 5. The isotherm curve
of APC-750@Pd (pink), APC-750 (blue), NPC-1000 (red),
and aZIF (black) is classified as type of IV isotherms
adsorption with an approximately vertical rise at low-
activation with KOH, the bonds at 449.3, 1056.4, 1542.3,
À1
and 2931 cm are related to the vibration of benzene
rings, C–C, C═C, and C–H stretching, respectively, on
APC-750. The incorporation of Pd with APC-750 was not
significantly changed IR spectra because Pd NPs do not
form any chemical bond with the APC-750.
The microstructural properties of as-synthesized
aZIF, NPC-1000, APC-750, and APC-750@Pd were char-
acterized by SEM and transmission electron microscopy
pressure ranges (P/P ꢁ 0), which suggests the formation
0
of the micropores and mesoporous on APC-750, APC-
750@Pd, NPC-1000, and aZIF, respectively. The pore size
distribution of APC-750 and APC-750@Pd shows that the
microporous is smaller than 3 nm. In addition, according
to the BET analyses, average particle sizes of all materials
synthesized are less than 60 nm (Table 1).
According to Table 1, aZIF has a lower BET surface
2
area of 102.29 m /g than NPC-1000 with a surface area of
2
2
1
37.34 m /g, APC-750 with a surface area of 832.11 m /g,
2
and APC-750@Pd with a surface area of 618.28 m /g, pre-
sumably due to an increase of density and relative to the
crystalline phase. The total pore volumes of the APC-750
and APC-750@Pd are greater than the pore volume of
aZIF and NPC-1000, indicates that the APC-750 and
APC-750@Pd are structurally different forms. The rela-
tively large pore volume and pore size of APC-750 can
FIGURE 2 Fourier transform infrared (FTIR) spectra of
amorphous zeolitic imidazolate framework (aZIF), NPC-1000, APC-
7
50, and APC-750@Pd

BUĞDAY ET AL.
5 of 15
FIGURE 3 Scanning
electron microscopy (SEM)
images of (a) amorphous zeolitic
imidazolate framework (aZIF),
(
(
b) NPC-1000, (c) APC-750,
d) elemental mapping analysis
of APC-750@Pd, and
e) transmission electron
(
microscopy (TEM) images of
APC-750@Pd
FIGURE 4 (a) Elemental
mapping analysis of 5-times used
APC-750@Pd, (c) N, (d) Pd,
(
e) C, (f) O. (b) The scanning
electron microscopy (SEM)
image of the 5-times used APC-
7
50@Pd
provide more host porous channels for the Pd
nanometals. In addition, the surface area and pore vol-
ume of the APC-750@Pd catalyst are found less than the
APC-750. This difference may be attributed to the place-
ment of Pd NPs on the surface and in the pores reduces
the BET surface area and pore volume.

6
of 15
BUĞDAY ET AL.
FIGURE 5 (a) N
2
adsorption isotherms of amorphous zeolitic imidazolate framework (aZIF), NPC-1000, APC-750, and APC-750@Pd at
7
7 K; (b) Barrett–Joyner–Halenda (BJH) analysis of aZIF, NPC-1000, APC-750, and APC-750@Pd
TABLE 1 Surface area, pore volume, and average adsorption pore width values of the aZIF, NPC-1000, APC-750, and APC-750@Pd
obtained from Brunauer–Emmett–Teller (BET) analysis
BET surface
area (m /g)
Pore volume
(cm /g)
Adsorption average pore width
(4 V/A by BET) (nm)
Average particle
size (nm)
2
3
Sample
aZIF
102.2902
137.3424
832.1132
618.2887
0.1025
0.1178
0.5753
0.3924
4.01
3.23
2.76
2.53
58.65
43.68
7.21
NPC-1000
APC-750
APC-750@Pd
9.70
Abbreviation: aZIF, amorphous zeolitic imidazolate framework.
both solvent molecules large cages and decomposition
of organic molecules. The total weight loss (72%) is equal
to 16 + 56% for the range from room temperature to
ꢀ
ꢀ
4
8
87 C. The third decline of the TG curve occurred at
50 C (16%) results in a total weight loss of (73%) is
related to the loss of the palladium metals. Decomposi-
ꢀ
tion of the network at over 850 C demonstrates
high thermal stability of the APC-750@Pd catalyst, which
is a highly desirable property of catalyst in catalytic
reactions.
The APC-750@Pd catalyst was investigated further by
X-ray photoelectron spectroscopy (XPS) analysis to show
the oxidation state of the elements (Figure 7). The exis-
tence of C(1s), N(1s), O(1s), and Pd (3d) peaks confirms
the catalyst structures. The N peaks at 397.3, 397.6, 399.4,
and 402.8 eV are divided into three peaks corresponding
FIGURE 6 The thermal gravimetric analysis (TGA) and
differential thermal analysis (DTA) of APC-750@Pd catalyst
[
63]
to pyridinic-N (397.3 and 397.6 eV),
pyrrolic-N
[
64]
[65]
The thermal gravimetric analysis (TGA) of the
(399.4 eV),
and graphitic-N (402.8 eV).
The binding
APC-750@Pd catalyst shows three main weight losses
energy observed between 283 and 290 eV corresponds to
the C(1s) in bonding forms of C–C, C–O, and C–N.
Figure 7e demonstrated that the Pd embedded in the
APC-750@Pd was present in the metallic state rather
than in the oxidation state with the bonding energies
observed at 335.2 and 340.2 eV for Pd 3d5/2 and 3d3/2
ꢀ
(Figure 6). The first decline of the TG curve below 220 C
can be ascribed to the mass loss of absorbed water or
solvent on the surface of catalyst (16%) and then a drastic
ꢀ
decomposition of APC-750@Pd from 345 to 487 C results
in a total weight loss of 72%, corresponding to the loss of

BUĞDAY ET AL.
7 of 15
FIGURE 7 X-ray
photoelectron spectra (XPS) of
APC-750@Pd catalyst, (a) C1s,
(
(
c) O1s and deconvolution of
b) N1s, (d) Pd3d
levels, respectively, and very sharp with a huge intensity.
These peaks are assigned to Pd 3d5/2 and 3d3/2.
3.2 | Catalysis
0
[66,67]
When schematic deconvolution of the Pd (3d) was exam-
ined in Figure 7d, the two minor peaks observed at 337.2
and 341.6 eV attributed to Pd 3d5/2 and 3d3/2, respec-
The catalytic activity of the APC-750@Pd catalyst was
investigated using the Suzuki–Miyaura cross-coupling
reaction for phenylboronic acid with different aryl
bromides. The reaction between 4-bromoanisole and
phenylboronic acid was selected as a model reaction to
explore optimum reaction conditions for the Suzuki–
Miyaura reaction catalyzed by APC-750@Pd catalyst
(Table 2).
2
+
0
tively. Based on this information, it is seen that both Pd
2
+
and Pd are present in the structure of the APC-750@Pd
catalyst. After reduction, the remaining Pd in the cata-
lyst structure may be attributed to the Pd located inte-
rior spaces of the APC-750.
2
+
2
+

8
of 15
BUĞDAY ET AL.
No product formation was observed on the reactions
in water in the absence of catalyst and base (Table 2,
Entries 1 and 2). Different type bases were used, and
solvents such as DMF, EtOH, i-PrOH, and dioxane and a
mixture of DMF:H O, EtOH:H O, and i-PrOH:H O were
2
2
2
investigated, and i-PrOH:H O was preferred as the sol-
2
moderate yields were obtained with Et N, KOH, NaOH,
vent from the view of yield and green chemistry (Table 2,
Entries 11–16). After selecting the base and solvent to be
used in the reaction, the effect of the catalyst concentra-
tion on the reaction yield was examined (Table 2, Entries
17–19). After the test reaction, 5 mg of the APC-750@Pd
(0.049 mmol% Pd) was found effective catalyst concentra-
tion in the Suzuki–Miyaura reaction. In addition, the
effect of the reaction temperature was investigated, and
3
and K PO4 bases, and good yields of reaction were
3
obtained with Cs CO and Na CO , and excellent yield of
2
3
2
3
the reaction was obtained with Na CO bases in i-PrOH/
2
3
ꢀ
water (1:2) mixture at 80 C (Table 2, Entries 4–10). The
type of base used is essential because of the instability of
the ZIF structure under basic conditions. Even if the type
of base used is important, the structural stability of the
support material in the base medium was good even in
reactions using strong bases. Thus, K CO was selected
ꢀ
80 C was found the optimum reaction temperature for
this reaction (Table 2, Entries 20–21). A 26% yield was
obtained in the homogeneously catalyzed Suzuki–
Miyaura reaction using the same amount of Pd (OAc)2
2
3
as the base for further treatments due to higher yields
[68]
and minimum structural deformations.
Then, different
TABLE 2 Optimization of the Suzuki–Miyaura cross-coupling reaction condition catalyzed by APC-750@Pd catalyst
a
Entry
Catalyst loading
-
Base
Solvent
Temp./time
Yield (%)
ꢀ
1
2
3
4
5
6
7
8
9
K
-
2
CO
3
H
H
H
H
H
H
H
H
H
2
2
2
2
2
2
2
2
2
O
O
O
O
O
O
O
O
O
80 C, 0.5 h
-
ꢀ
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
5 mg
1 mg
2 mg
4 mg
5 mg
5 mg
80 C, 0.5 h
-
ꢀ
KOH
Et
NaOH
PO
CO
CO
80 C, 0.5 h
70
60
67
62
60
65
80
65
85
89
63
85
93
99
34
52
81
-
ꢀ
3
N
80 C, 0.5 h
ꢀ
80 C, 0.5 h
ꢀ
K
3
4
80 C, 0.5 h
ꢀ
Cs
2
3
80 C, 0.5 h
ꢀ
Na
2
3
80 C, 0.5 h
ꢀ
K
K
K
K
K
K
K
K
K
K
K
K
K
K
K
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
80 C, 0.5 h
ꢀ
10
11
12
13
14
15
16
17
18
19
20
21
22
23
DMF
80 C, 10 min
ꢀ
EtOH
80 C, 10 min
ꢀ
i-PrOH
Dioxane
80 C, 10 min
ꢀ
80 C, 10 min
ꢀ
H
H
H
H
H
H
H
H
H
H
2
2
2
2
2
2
2
2
2
2
O/DMF (2:1, v/v)
O/EtOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
O/i-PrOH (2:1, v/v)
80 C, 10 min
ꢀ
80 C, 10 min
ꢀ
80 C, 10 min
ꢀ
80 C, 10 min.
ꢀ
80 C, 10 min..
ꢀ
80 C, 10 min..
rt, 1 h.
ꢀ
50 C, 10 min.
58
26
58
ꢀ
Pd (OAc)
Pd (OAc)
2
2
, 0.1 mg; PPh3 0.413 mg
, 0.1 mg
80 C, 10 min.
ꢀ
80 C, 10 min.
a
Reaction conditions: phenylboronic acid (0.6 mmol), 4-bromoacetophenone (0.5 mmol), base (1.0 mmol), solvent 3 mL. GC yields determine according to
-bromoanisole using (trifluoromethyl)benzene as an internal standard.
4

BUĞDAY ET AL.
9 of 15
TABLE 3 Suzuki–Miyaura cross-coupling reactions catalyzed by APC-750@Pd catalyst
a
Entry
ArB (OH)
2
ArX
Product
Time
Yield (%)
1
7 min
100
2
3
10 min
12 h
99
50
4
5
6
7
8
9
10 min
10 min
5 min
99
99
99
85
70
100
5 min
5 min
20 min
1
0
30 min
27
(
Continues)

10 of 15
BUĞDAY ET AL.
TABLE 3 (Continued)
Entry ArB (OH)
a
2
ArX
Product
Time
Yield (%)
1
1
20 min
96
1
1
2
3
30 min
30 min
43
99
1
4
30 min
99
1
1
1
1
1
2
5
6
7
8
9
0
30 min
30 min
15 min
15 min
15 min
30 min
99
99
100
100
99
85

BUĞDAY ET AL.
11 of 15
TABLE 3 (Continued)
a
Entry
ArB (OH)
2
ArX
Product
Time
Yield (%)
2
1
30 min
16
2
2
60 min
15
2
2
2
2
3
4
5
6
30 min
10 min
30 min
5 min
99
53
45
65
2
2
2
7
8
9
5 min
5 min
5 min
48
36
74
3
0
60 min
8
(
Continues)

12 of 15
BUĞDAY ET AL.
TABLE 3 (Continued)
Entry ArB (OH)
a
2
ArX
Product
Time
Yield (%)
3
1
2
60 min
-
3
60 min
-
3
3
60 min
-
a
Reaction conditions: APC-750@Pd (5 mg, 0.049 mmol%Pd), phenylboronic acid (0.6 mmol), 4-bromoacetophenone (0.5 mmol), K
O 3 mL (1:2). GC yields determine according to arylbormides using (trifluoromethyl)benzene as an internal standard.
2
CO
3
(1.0 mmol), i-PrOH/
H
2
(
0.049 mmol) with PPh as a ligand (Table 2, Entry 22).
produced after 12 h (Table 3, Entry 3). It is worth men-
tioning that no homocoupling product was obtained
using APC-750@Pd as a catalyst. Also, the aZIF structure
and its activated derivatives can increase the specific sur-
3
However, a 58% yield was obtained using the same
amount of Pd (OAc)2 (0.049 mmol) without PPh3
(Table 2, Entry 23). These results show the efficiency of
[69]
the APC-750@Pd catalyst.
face area of the catalyst to increase the reaction yields.
The optimization reaction condition on hand, the
It can consider that the role of APC-750 is material diffu-
sion to the active site of catalyst and creates a high spe-
cific surface contains nano Pd particles.
Suzuki–Miyaura cross-coupling reaction of different aryl
bromides
with
phenylboronic
acid
and
4
-floropehnylboronic acid, was examined in order to
The reusability of the catalyst was examined in the
coupling of 4-bromoacetophenone with PhB (OH)2
(Table 4). For this purpose, after each reaction, catalyst
was removed from reaction media by centrifuge and pre-
pared for the next run by washing with 2-propanol/water
obtain biologically important different arylated com-
pounds (Table 3). As shown in Table 3, different
substituted biaryl derivatives were obtained in good to
excellent yields in less than 30 min with aryl bromides.
Both electron-rich and electron-poor substituted with
ꢀ
and dried at 80 C for 3 h. The results show that the APC-
–
CN, –NO , –COCH , –CH , –OCH , F, –CH , and –CF
750@Pd catalyst can be used up to five times with a %15
decrease in its catalytic performance.
2
3
3
3
3
3
aryl bromides afforded the biaryl products in excellent
yields. However, with electron-rich aryl bromides, higher
yields were obtained. The Suzuki cross-coupling reaction
of the electron-rich or electron-poor aryl bromides with
the –F, –C (CH ) , substituted phenylboronic acid takes a
A filtration test was performed. The amount of
leached Pd was determined by ICP-MS analysis to under-
stand whether the palladium is leaching from the catalyst
structure while performing the reaction. For this aim, the
reaction of 4-methoxybenzene with phenylboronic acid
was chosen. Three minutes after starting the reaction, the
catalyst was removed from the reaction medium by cen-
trifuge. Meanwhile, the sample taken from the reaction
medium was analyzed by gas chromatography (GC).
Then, the rest solution without APC-750 catalyst was
3
3
longer reaction time than the phenylboronic acid
(Table 3, Entries 13–20). The cross-coupling reaction of o-
substituted aryl bromides with both boronic acid deriva-
tives needs more reaction time due to the substituted
group's steric hindrance (Table 3, Entries 10, 11, 21, and
2
4
2). This catalytic system also was tested on
-chloroacetophenone, and moderate yields were
ꢀ
stirred for a further 5 min at 80 C. According to the GC

BUĞDAY ET AL.
13 of 15
results of both samples, the 32% and 33% yield was
obtained after the 5th and 10th minutes, respectively.
From the hot filtration test results, it concludes that the
Pd metal did not leach out at the first run. Thanks to
APC-750, the catalyst seems to be very stable under these
reaction conditions. According to ICP-MS analysis, there
is no Pd metal in the solution after the first use of the cat-
alyst. To validate the room temperature filtration test, the
Pd amount in the 5-times used catalyst was determined
by ICP-MS analysis and found a value (0.96 wt% Pd) less
than the initial amount (1.068 wt% Pd). The minimum
leaching ratio of the active metal from the support mate-
rial is the prime property in heterogeneous catalysis.
In addition to the hot filtration test, the poisoning
tests were performed using PVP to determine the homo-
geneity/heterogeneity nature of catalysis described here.
According to this poison test, any leached nano Pd parti-
cles in the solution will be captured by PVP ligand. The
PVP ligand will inhibit Pd-NP activity in the solution,
which can show homogeneous activity. When some of
the nano-Pd particles leach from the catalyst structure,
both heterogeneous (supported) and homogeneous
(leached) catalyzed suzuki-Miyaura reaction can arise.
Herein, the PVP ligand was used for this purpose. The
addition of the large amount of PVP to the Suzuki–
Miyaura reaction of 4-bromoanisole with PhB (OH) did
2
not stop the reaction and not changed the amount of the
obtained reaction yield before. This experiment confirms
that the Suzuki–Miyaura reaction was heterogeneously
catalyzed by APC-750@Pd catalyst.
TABLE 4 Recyclability of the APC-750@Pd catalyst for the
Suzuki–Miyaura cross-coupling reaction
In order to show the efficiency of the APC-750@Pd
catalyst on the synthesis of biaryls, the activity of the
APC-750@Pd catalyst was compared with heterogeneous
palladium catalysts in Suzuki–Miyaura cross-coupling
[
70–79]
reactions.
It shows that the APC-750@Pd catalyst
has shown better catalytic activity than reported structur-
ally similar catalysts in case of reaction conditions, cata-
lyst concentration, and yields (Table 5). In the
a
Entry
Catalyst
Yield (%)
1
2
3
4
5
6
Fresh catalyst
Reused Run 1
Reused Run 2
Reused Run 3
Reused Run 4
Reused Run 5
99
99
97
93
88
85
[
70–79]
literature,
most of the Suzuki–Miyaura cross-
coupling reactions catalyzed by similar types of catalysts
require a high amount of catalyst loadings than our cata-
lytic system. Although our catalytic system works well
with aryl bromides, developed catalytic system does not
have the same effect with 4-chloroacetophenone.
In a word, our catalyst showed extraordinary catalytic
activity when considering the reaction parameters such
as catalyst loading, high efficiency with aryl bromides,
and short reaction time.
a
Reaction conditions: APC-750@Pd (5 mg, 0.049 mmol%Pd), phenylboronic
acid (0.6 mmol), 4-bromoacetophenone (0.5 mmol), K CO (1.0 mmol), i-
PrOH/H O 3 mL (1:2). GC yields determine according to arylbormides using
trifluoromethyl)benzene as an internal standard.
2
3
2
(
TABLE 5 Comparison of ZPC-750@Pd in the Suzuki–Miyaura reaction of 4-bromoacetophenone with phenylboronic acid with reported
catalysts
Catalyst
Solvent/base/temp./Pd loading
Time (min)
Yield (%)
Ref.
ꢀ
[70]
Fe@Pd/C
H
H
2
2
O/K
O/K
2
2
CO
3
3
/80 C/0.5 mol%
60
20
60
60
45
30
600
60
15
360
7
90
97
95
96
96.3
96
97
91
94
94
99
Tang et al.
ꢀ
[71]
Pd/C
CO
/100 C/1.5 mol%
Rao et al.
ꢀ
[72]
[73]
N-doped NPC-Pd
N-doped PC-900-Pd
MOF-5-NPC-900-Pd
PdNPs/CMK-3
Pd@mesoporous carbon
Pd@A-ZIF-8
EtOH–H
EtOH–H
EtOH–H
EtOH–H
2
2
2
2
O/K
O/K
O/K
O/K
2
2
2
2
CO
CO
CO
3
3
3
3
/25 C/0.2 mol%
Zhang et al.
Zhang et al.
ꢀ
/25 C/0.2 mol%
ꢀ
[74]
/25 C/0.1 mol%
Dong et al.
ꢀ
[75]
CO
/40 C/0.1 mmol%
Liu et al.
ꢀ
[76]
H
2
O/K
EtOH–H
O/K CO
DMF/K CO
i-PrOH–H O/K
2
CO
3
/100 C/10 μequiv.
Enneiymy et al.
[77]
ꢀ
2
O/K
3
PO
4
/70 C/0.1 mol%
Dabiri et al.
ꢀ
[78]
Pd-NHC-MIL-101(Cr)
Pd-loaded silica
APC-750@Pd
H
2
2
3
/85 C/0.6 mol%
Niknam et al.
ꢀ
[79]
2
3
/100 C
Sarkar et al.
This work
ꢀ
2 3
CO /80 C/0.049 mmol%
2

14 of 15
BUĞDAY ET AL.
4
| CONCLUSIONS
ARKIVOC 2018, part v; i) E. O. Karaca, M. Akkoç, M. N.
Tahir, C. Arıcı, F. Imik, N. Gürbüz, S. Ya s¸ ar, I. Ozdemir, Tetra-
hedron Lett. 2017, 58, 3529; j) F. Imik, S. Ya s¸ ar, I. Ozdemir,
J. Organomet. Chem. 2009, 896, 162; k) F. Imik, S. Ya s¸ ar, I.
Ozdemir, Inorg. Chim. Acta 2019, 495, 118969.
In conclusion, we have designed Pd NP-doped porous
carbon material synthesized from amorphous ZIF mate-
rial. The catalytic efficiency of Pd-doped porous carbon
material was investigated in Suzuki–Miyaura cross-
coupling reactions, and high yields were obtained with a
low catalyst concentration. Also, the reusability of the
catalyst was checked, and the catalytic activity dropped
[
10] T. E. Barder, S. D. Walker, J. R. Martinelli, S. L. Buchwald,
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[
[
1
5% after five consecutive reaction runs. This catalytic
system has features that stand out in many ways, such as
recyclability of catalyst, little reaction times, and excel-
lent yields with workup render. Therefore, this catalytic
protocol is more attractive and economically viable.
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15] V. Polshettiwar, C. Len, A. Fihri, Coord. Chem. Rev. 2009, 253,
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16] a) M. Akkoç, N. Bu ꢀg day, S. Altın, S. Ya s¸ ar, Appl. Organomet.
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S. Ya s¸ ar, I. Ozdemir, J. Organomet. Chem. 2021, 943, 121823.
ACKNOWLEDGMENT
_
[17] A. Gniewek, J. J. Ziolkowski, A. M. Trzeciak, M. Zawadzki, H.
Inönü University Research Council partially supported
Grabowska, J. Wrzyszcz, J. Catal. 2008, 254, 121.
the study by the project number of FCD-2021-2557.
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[
18] V. Udayakumar, A. Pandurangan, RSC Adv. 2015, 5, 78719.
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CONFLICT OF INTEREST
The authors declare that they have no known competing
financial interests or personal relationships that could
have appeared to influence the work reported in this
paper.
[
[
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ORCID
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Nesrin Bu ꢀg day https://orcid.org/0000-0002-3882-035X
Serdar Altın https://orcid.org/0000-0002-4590-907X
Sedat Ya s¸ ar https://orcid.org/0000-0001-7285-2761
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