Facile Synthesis of a High Performance NiPd@CMK-3 Nanocatalyst for Mild Suzuki-Miyaura Coupling Reactions

Article abstract of DOI:10.1002/cctc.201801872

Highly dispersed nickel-palladium bimetallic nanoparticles (～2 nm) on ordered mesoporous carbon CMK-3 (NiPd@CMK-3) were simply prepared using a co-infiltration method of the metal salts. The nanoparticles were successfully applied to the mild Suzuki-Miyaura coupling reactions at 25～50 °C using 4-bromoanisole and phenylboronic acid, and showed excellent catalytic performance with the high activity (0.521×10^?3 mol_c ? g_am^?1 ? s^?1) and productivity (69.1 g_p ? g_cat^?1 ? h^?1).

Full text of DOI:10.1002/cctc.201801872

Accepted Article
Title: Facile synthesis of high performance NiPd@CMK-3 nanocatalyst
for mild Suzuki-Miyaura coupling reactions
Authors: Ji Chan Park, Aram Kim, Sanha Jang, Jung-Il Yang, Shin
Wook Kang, Chan-Woo Lee, Byung-Hyun Kim, and Kang
Hyun Park
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To be cited as: ChemCatChem 10.1002/cctc.201801872
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10.1002/cctc.201801872
ChemCatChem
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Facile synthesis of high performance NiPd@CMK-3 nanocatalyst
for mild Suzuki-Miyaura coupling reactions
Ji Chan Park,‡a Aram Kim,‡b Sanha Jang,b Jung-Il Yang,a Shin Wook Kang,a Chan-Woo Lee,c Byung-
Hyun Kim,*,c Kang Hyun Parkb,*
Abstract: Highly dispersed nickel-palladium bimetallic nanoparticles
(~2 nm) on ordered mesoporous carbon CMK-3 (NiPd@CMK-3) were
simply prepared using a co-infiltration method of the metal salts. The
nanoparticles were successfully applied to the mild Suzuki-Miyaura
coupling reactions at 25
~
50 oC using 4-bromoanisole and
phenylboronic acid, and showed excellent catalytic performance with
the high activity (0.521×10-3 molc·gam-1·s-1) and productivity (69.1
gp·gcat-1·h-1).
Scheme 1. Synthetic procedures for NiPd@CMK-3 nanocatalyst.
practical aspect. Therefore, highly metal-loaded catalysts (above
20 wt%) are needed with high and uniform dispersion on a
support; such materials have large pore volume and porosity,
leading to an increased number of active sites. However, noble
metals are generally restricted to low load of the active sites,
mainly due to their high prices. Reducing dosage of expensive Pd
metal has been a major challenge for an economical reasons.[22-
25] In particular, mixing other elements with the precious Pd metal
can modulate the elemental distribution on the surface, the
intermetallic charge transfer, and the lattice strain.[26-28] In recent
years, NiPd bimetallic particles have shown their enhanced
catalytic activity, even higher than that of single metal Pd particles,
for carbon coupling reactions.[29-33] Although the results for
synergistic effects of NiPd nanoparticles in carbon coupling
reactions have been reported, the mechanisms and theoretical
explanations for the enhanced activity of NiPd alloys are rare and
still ambagious.[34,35] In addition, the preparation processes for
NiPd bimetallic nanostructures are complicated.[36,37]
Due to their easy separation, good reusability, and
environmental compatibility, solid catalysts have been widely
used in various organic reactions.[1] Many studies on catalyst
synthesis have been performed to enhance the catalyst activity
and stability by manipulating morphology and active sites, but
maximization of catalyst productivity still remains as a challenge
in the heterogeneous catalytic reactions.[2-5] To find a high
performance catalyst, high dispersion of active nanoparticles and
high load of active metals are necessary, and can generally be
achieved by well-defined physical protection materials such as
metal-oxides (silica, alumina, and titania) and carbons (carbon
nanotube, graphene, and activated carbon) to prevent active
particle aggregation and agglomeration.[6-10]
The Suzuki-Miyaura coupling reaction, which creates new
carbon-carbon bonds between organohalides and boronic acid
derivatives, has been utilized for the production of fine chemicals,
polymers, and pharmaceutical products, using palladium (Pd)-
based catalysts in alkaline condition.[11-13] Typically,
heterogeneous Pd nanocatalysts such as Pd nanoparticles (NPs),
Pd/C, Pd/SiO2, and Pd/Al2O3 have been applied to the reaction.[14-
Herein, we report a new synthetic method for surfactant-free
NiPd bimetallic nanoparticles with high dispersion and high
content of active sites (20 wt%) in the pores of CMK-3. The
catalyst shows good activity of 0.521×10-3 molc·gam-1·s-1 under the
o
19]
mild Suzuki-Miyaura coupling reaction at 25 C, as well as very
Recently, an ordered mesoporous carbon (CMK-3) with high
high productivity (69.1 gp·gcat-1·h-1) compared to those of other
conventional catalysts. Furthermore, the high catalytic property of
the NiPd bimetallic surfaces can be interpreted based on
computational simulations.
surface areas, pore volumes, and uniform pore sizes has been
introduced as a catalyst support, providing good reactant diffusion
surroundings and enhanced durability for the active sites.[20,21]
In heterogeneous catalytic reactions, increase of product yield
per unit the catalyst weight has a significant meaning from a
First, CMK-3 was prepared using a silica template SBA-15, as
reported in elsewhere.[38] Next, the NiPd bimetallic nanoparticles
were easily synthesized via a simultaneous infiltration of nickel
nitrate hexahydrate and palladium nitrate dihydrate into the pores
of the CMK-3 and subsequent thermal reduction under a
hydrogen gas flow (Scheme 1). During the process, it was
possible to form the nanoparticles through the pore confinement
effect. The TEM image shows extremely tiny NiPd nanoparticles
as black dots in the nano-channels of CMK-3 (Figure 1a). The
high-resolution TEM (HRTEM) image indicates the uniform NiPd
nanoparticles around 2 nm (Figure 1b). The distance between
adjacent lattice fringe images was measured and found to be 0.22
nm, which corresponded to the (111) plane of face-centered-cubic
(fcc) NiPd alloy (Figure 1c). The high-angle annular dark-field
[a]
[b]
Dr. J. C. Park, Dr. J.-I. Yang, Dr. S. W. Kang,
Clean Fuel Laboratory,
Korea Institute of Energy Research, Daejeon, 34129, Korea
Dr. A. Kim, S. Jang, Prof. K. H. Park
Department of Chemistry and Chemistry Institute for Functional
Materials,
Pusan National University, Busan, 46241, Korea
E-mail: chemistry@pusan.ac.kr
[c]
Dr. C. W. Lee, Dr. B. H. Kim,
Platform Technology Laboratory,
Korea Institute of Energy Research, Daejeon, 34129, Korea
E-mail: bhkim@kier.re.kr
‡ These authors contributed equally to this work.
Supporting information for this article is given via a link at the end
of the document.
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Figure 2. (a) TEM and (b) HAADF-TEM images of Ni@CMK-3, (c) TEM and (d)
HAADF-TEM images of Pd@CMK-3, and (e) XRD spectra of Ni@CMK-3,
Pd@CMK-3, and NiPd@CMK-3 catalysts. All bars represent 50 nm.
observed between 2θ = 40.1o of Pd (111) and 44.5o of Ni (111).
This shift indicates Pd lattice contraction caused by replacing fcc
Pd atoms with Ni atoms. Using the Scherrer equation, the crystal
sizes of Ni, Pd, and NiPd nanoparticles in the catalysts were
calculated and found to be 1.5, 2.8, 1.6 nm, respectively. These
values are well-matched to the particle sizes in the TEM images.
To characterize the porous structures of the catalyst, the N2
adsorption/desorption isotherms were obtained. Both the pristine
CMK-3 and NiPd@CMK-3 exhibited type IV adsorption–
desorption hysteresis, indicating preservation of the mesoporous
structure after NiPd formation in CMK-3 (Figure 3a). The BET
surface areas and total pore volumes were 1433.5 m2∙g−1 and
1.45 cm3∙g-1 for the CMK-3, and 862.4 m2∙g−1 and 0.91 cm3∙g-1 for
the NiPd@CMK-3 nanocatalyst. Using the Barrett–Joyner-
Halenda (BJH) method, average pore sizes of CMK-3 and
NiPd@CMK-3 were estimated from the desorption branches of N2
isotherms and found to be equal at 5.3 nm (Figure 3b). The
alloyed NiPd loading of the NiPd@CMK-3 was 18.74 wt% (Ni:
9.71 wt%, Pd: 9.03 wt%), as determined by inductively coupled
plasma-atomic emission spectrometry (ICP-AES), which is a
good match with the nominal metal loading value of 20 wt%.
The CMK-3 supported NiPd bimetallic nanoparticles were
employed in the Suzuki-Miyaura coupling reactions. First, the
reactions using 4-bromoanisole and phenylboronic acid were
performed with screening some solvents and bases under
different temperature conditions (Table S1-2, see the ESI†).
Methanol and ethanol as protic solvents led to higher conversions
of 4-bromoanisole as a substrate than those of other organic
solvents such as dimethylformamide (DMF), dimethyl sulfoxide
(DMSO), dimethylacetamide (DMAc), 1,4-dioxane, acetonitrile,
Figure 1. (a) Low-resolution TEM, (b-c) HRTEM, (d) HADDF-TEM, and (e-h)
scanning TEM images with elemental mapping (Ni, Pd, C, and all) of
NiPd@CMK-3 nanocatalyst. The bars represent 50 nm (a, d-h) and 5 nm (b, c).
(HAADF)-TEM and the corresponding elemental mapping
images of NiPd@CMK-3 nanocatalyst demonstrate high
dispersity of Ni and Pd elements incorporated throughout the
mesopores of CMK-3 (Figure 1d-h). After thermal treatment, Pd
and Ni were each loaded at 10 wt% on the basis of the metals
converted from the metal salts.
For comparison of the characteristics of NiPd@CMK-3, the
Ni@CMK-3 and Pd@CMK-3 nanocatalysts were also prepared
by sole infiltration of the single metal salt with each metal having
a loading amount of 10 wt%. The TEM and HAADF-TEM images
show the Ni nanoparticles with diameters of approximately 2 nm;
nanoparticles are well-incorporated in the pores of CMK-3 (Figure
2a-b). The Pd nanoparticles, incorporated into the mesopores of
CMK-3, were observed to be around 3 nm (Figure 2c-d). The
phases and crystallite sizes of Ni@CMK-3, Pd@CMK-3, and
NiPd@CMK-3 nanocatalysts were analysed using X-ray
diffraction (XRD) spectra (Figure 2e). The XRD patterns of the
Ni@CMK-3 and Pd@CMK-3 were indexed to the face-centered-
cubic (fcc) Ni (JCPDS No. 04-0850) and fcc Pd (JCPDS No. 46-
1043), respectively. The diffraction peak of NiPd@CMK-3 was
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Table 1. Suzuki-Miyaura reaction data using the NiPd@CMK-3 nanocatalyst for
various aryl halides and aryl boronic acids.a)
Figure 3. (a) N2 adsorption/desorption isotherms of pristine CMK-3 and
NiPd@CMK-3, and (b) pore size distribution diagrams calculated from
desorption branches using the BJH method.
toluene, and tetrahydrofuran. Using mixed solvents with water,
conversion rates were found to increase more, because water as
a co-solvent can facilitate dissolution of K2CO3 as a base and
contribute to protolytic decomposition of an organoboron
compounds. In the base effect, KOH and NaOH, which are highly
soluble in water, showed high conversion rates (> 96%),
compared to the value (72 %) of KHCO3 and NaHCO3. As
expected, higher conversion rates were obtained, increasing the
reaction temperatures in the range of 25–75 oC.
a) The reaction tests were conducted at 50 oC for 1h with aryl halide (0.5 mmol),
arylboronic acid (0.6 mmol), K2CO3 (1.0 mmol), NiPd@CMK-3 (2.7 mg), and
ethanol/H2O (1:1). Conversion rates were determined using GC-MS
spectrometry.
Furthermore, several substrates for the Suzuki-Miyaura
coupling reactions were tested using several aryl halides and aryl
boronic acid. The NiPd@CMK-3 nanocatalyst exhibited high
conversion rates (>92%) for various aryl halides and aryl boronic
acid substitutes involving electron-withdrawing and electron-
donating groups (Table 1). Bromobenzenes bearing methyl,
hydroxyl, fluoride, and aldehyde, and phenylboronic acid with
substituents were successfully converted to the biaryl products.
To compare the activity of NiPd@CMK-3 nanocatalyst, Pd (20
wt%)@CMK-3 was tested under the same reaction conditions
(Figure 4a). The catalyst activity was noted to exhibit site-time-
yield (the number of 4-bromoanisole moles converted to 4-
methoxybiphenyl per gram of active metals per second). For the
NiPd@CMK-3 catalyst containing 20 wt% of NiPd alloy, the
activity was calculated to be 0.521 mmol·gam-1·s-1 higher than the
activity (0.495 mmol·gam-1·s-1) of pure Pd@CMK-3 (Pd: 20wt%)
(Figure 4b). To the best of our knowledge, this is a record-high
value among the reported activity data so far (Table S3). The
catalyst productivity [product yield (g) per catalyst weight (g) per
hour] was calculated. As expected, the NiPd@CMK-3 catalyst
showed a high productivity (69.1 gp·gcat-1·h-1) (Figure 4c). The
catalyst had a much higher value than those of other previously
previously reported other catalysts (0.2 ~ 28.2 gp·gcat-1·h-1 , Table
S3). On the other hand, the Pd based catalysts showed the lower
productivity values [56.3 gp·gcat-1·h-1 at Pd(10 wt%)@CMK-3, 65.7
gp·gcat-1·h-1 at Pd(20 wt%)@CMK-3, Table S3].
Although the active metal contents (Ni: 10wt%, Pd: 10wt%) in
the NiPd@CMK-3 nanocatalyst were high compared to those of
the conventional catalysts, the high activity of the catalyst due to
the small and active NiPd bimetallic nanoparticles in CMK-3 can
lead to the enhanced productivity, making this material very
advantageous for future commercial applications.
To understand the origin of higher activity of the NiPd@CMK-3
nanocatalyst in the Suzuki-Miyaura coupling reaction, the
catalytic property of the NiPd@CMK-3 nanocatalyst was newly
elucidated by theoretical data based on computational
simulations. Electronic structure and charge transfer calculations
were performed using the density functional theory (DFT).
Generally, it is known that the synergetic effects in bimetallic
alloys can be ascribed to the modified electronic structures and
the corresponding charge transfer mechanism.
Model structures for Pd nanocatalyst as a reference model and
two representative bimetallic NiPd nanocatalysts were prepared:
1) a clean Pd (111) surface, 2) a Pd (111) surface where a Ni layer
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Table 2. Adsorption energies of 4-bromoanisole on different surfaces and
charge differences of Br before/after the adsorption.
System
Eads (eV)
Δ Charge (e, Bader)
Br
Substrate
Pd (111)
–0.42
–0.51
–0.80
–0.002
–0.044
–0.110
+0.034
+0.062
+0.061
Pd covered NiPd (111)
Ni covered NiPd (111)
Figure 4. (a) Applied Suzuki-Miyaura coupling reaction, and (b) catalytic activity
and (c) productivity data of the catalysts. The reactions were conducted with 4-
bromoanisole (1.25 mmol), phenylboronic acid (1.50 mmol) and K2CO3 (2.50
mmol) at 25 oC for 1 h. (gam= active metal content, molc=converted 4-
bromoanisole mol, gp=product weight, gcat=total weight of active metal and
supporting material)
is located below a surface layer of Pd, and 3) a Pd (111) surface
covered with a Ni layer (Figure S1). Then, a 4-bromoanisole
molecule was placed on the surfaces of our model structures
since the first step of the Suzuki-Miyaura coupling reaction should
be an adsorption of 4-bromoanisole on the surfaces of catalysts
[34]. It is also known that the first step which is the oxidative
addition of an aryl halide to a catalyst is generally the rate
determining step of the reaction.[39] The adsorption site was
chosen to be the hollow-hcp site, which is the most stable
adsorption site among the hollow-fcc, hollow-hcp, bridge and
parallel sites (Table S4). The adsorption site was chosen to be
the hollow-fcc site. The adsorption energy of 4-bromoanisole on
different surfaces, Eads, was calculated using the following
equation:
Figure 5. Geometry optimized structures for 4-bromoanisole adsorbed on a Pd
(111) surface and a Ni covered NiPd (111) substrate. The blue arrow is a
schematic diagram indicating a direction and an amount of electron charge
transfer from the substrate to Br in 4-bromoanisole. The number next to the Br
atom (yellow) is the Bader charge difference before and after the adsorption.
To check the catalyst stability and recyclability, the
NiPd@CMK-3 nanocatalyst was separated after reaction. The
NiPd/CMK-3 nanocatalysts were run four times. Although gradual
and partial degradation was revealed, the rapid deactivation was
not detected. The conversion rates were gradually decreased
from >99% of the fresh catalyst to ~84% of the recovered catalyst
applied in the 4th run (Figure S2). It would be attributed to the
reduced active surface areas by increased particle sizes (Figure
S2c). The partially dissolved NiPd alloy particles during the
reaction led to the formation of more increased particles
compared to the original particles as shown in Figure S2a-c.
Eads = E(bromoanisole/substrate) – [E(bromoanisole) + E(substrate)
]
where E(bromoanisole/substrate) is the total energy of the system after
an adsorption of 4-bromoanisole, E(bromoanisole) is the energy of an
isolated 4-bromoanisole molecule, and E(substrate) is the energy of
a clean surface. The calculated Eads of the bimetallic NiPd
surfaces was –0.51 eV for Pd covered NiPd (111) and –0.80 eV
for Ni covered NiPd (111), respectively, while Eads for the clean
Pd surface was –0.42 eV (Table 2). Since the chemical reaction
start with the adsorption process, the higher Eads could be
beneficial to the reaction.[40]
The theoretical results of adsorption energy calculations are in
good agreement with the experimental results showing the higher
activity of the NiPd@CMK-3 nanocatalyst than that of the Pd
nanocatalyst in the Suzuki-Miyaura coupling reaction. To clarify
the observed adsorption behaviors, we further quantified the
charge transfer from the substrate to Br in the 4-bromoanisole
molecule. The charge differences of Br between before and after
the adsorption of bromoanisole were found to be –0.002 e, –0.044
e, and –0.110 e for clean Pd (111), Pd covered NiPd (111), and
Ni covered NiPd (111) and, respectively. Consequently, the more
charges transferred from the substrate to Br in 4-bromoanisole,
the stronger adsorption of 4-bromoanisole on the catalysts occurs,
so that the bimetallic NiPd nanocatalysts are energetically more
favorable for the first step of the Suzuki-Miyaura coupling reaction,
leading to the higher activity (Figure 5).
Conclusions
In conclusion, the NiPd@CMK-3 nanocatalyst, bearing
surfactant-free NiPd nanoparticles (2 nm), was simply prepared
with a co-infiltration of mixed metal salts and subsequent thermal
treatment. The high metal load (Ni: 10 wt%, Pd: 10 wt%) and
dispersion of the catalyst could contribute to increased
productivity and to securing the particle stability for the Suzuki-
Miyaura coupling reactions. In addition, from the result of the
computational simulations, it was revealed that the NiPd
bimetallic particles had a stronger adsorption characteristic, with
higher charge transfer to 4-bromoanisole, than that of solitary Pd
particles, supporting the experimental data. It is anticipated that
this synthetic strategy for bimetallic NiPd will be applied to other
transition metal-noble metal hybrid nanocatalysts, such as CMK-
3 supported CoPd, FePd, NiPt, etc., for catalytic reactions.
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Suzuki coupling reaction tests For the typical reaction test, the
catalyst, 4-bromoanisole, phenylboronic acid, ethanol, water, and
potassium carbonate were added to a 10 mL glass vial with an aluminium
seal. The mixture was vigorously stirred for 1 h. After that, the reaction
mixture was filtered, washed with saturated aqueous sodium bicarbonate
solution, and extracted with dichloromethane. The organic layer was
concentrated under reduced pressure. The conversion rate of 4-
bromoanisole was determined using gas chromatography-mass (GC-MS)
spectrometry.
Experimental Section
Materials and methods
Chemicals Pluronic P123 (Mw=5,800), tetraethyl orthosilicate (TEOS,
98%), hydrofluoric acid (HF, 48 wt%), nickel nitrate hexahydrate
(Ni(NO3)2∙6H2O, ACS reagent, ≥ 98%), palladium(II) nitrate dihydrate
(Pd(NO3)2∙2H2O, ~ 40% Pd basis), sucrose and were purchased from
Aldrich. Hydrochloric acid (HCl, 35 wt%) and sulfuric acid (H2SO4, 95
wt%) were purchased from Junsei. All chemicals were used as received
without further purification..
Characterization High resolution transmission electron microscopy
(TEM) analysis was performed using a Tecnai TF30 ST and a Titan Double
Cs corrected TEM (Titan cubed G2 60-300). Energy-dispersive X-ray
spectroscopy (EDS) elemental mapping data were collected using a higher
efficiency detection system (Super-X detector). High power powder-XRD
(Rigaku D/MAX-2500, 18 kW) was also used for the analysis. N2-sorption
isotherms were obtained at 77 K with a Tristar II 3020 surface area
analyser.
Preparation of CMK-3 The mesoporous carbon (CMK-3) was prepared
by replication of mesoporous silica template (SBA-15). The SBA-15 was
prepared using a hydrothermal method. Typically, pluronic P123 (16.0 g)
was dissolved in distilled water (120 g) and HCl (2.0 M, 480 g) solution
with stirring at 35 °C for 1 h. TEOS (34.0 g) was added into the mixture
solution and aged for 24 h at 40 °C. After that, the reaction mixture was
then transferred to a Teflon-lined autoclave and aged at 150 °C for 24 h.
White powder was recovered through filtration and subsequently washed
with water, ethanol, and acetone. The product was completely dried in an
oven at 100 °C for 6 h, and was calcined at 550°C for 5 h in air to yield
SBA-15. The obtained SBA-15 (3.0 g) was added into the carbon precursor
solution prepared by dissolving sucrose (4.1 g) and H2SO4 (0.5 g) in
distilled water (15.0 g). The mixture was placed in an oven at 100°C for 6
h and subsequently aged at 160 °C for 2 h. After that, sucrose (2.5 g),
H2SO4 (0.3 g), and distilled water (15.0 g) were additionally added into the
aged mixture. The sample was carbonized at 800°C and maintained at that
temperature for 2 h under N2 flow (0.2 L∙min-1). Finally, to remove the silica
template, the carbon–silica composite was washed with HF solution (2.0
M, 100 g) at room temperature. The product was filtered, washed with
ethanol, and thermally treated at 400 °C for 4 h under N2 flow (0.2 L∙min-
1).
Acknowledgements
This research was supported by the Research and Development
Program of the Korea Institute of Energy Research (KIER) (No.
B9-2461-01) and funded by the Ministry of Trade, Industry and
Energy (MOTIE) of the Republic of Korea (No. 10050509). A. Kim
and K. H. Park were supported by Basic Science Research
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Science, ICT & Future Planning
(2017R1A4A1015533 and 2017R1D1A1B03036303).
Keywords: Nickel • Palladium • Bimetallic • Alloy • Catalyst •
Suzuki Coupling Reaction
Synthesis of NiPd@CMK-3 nanocatalyst To prepare the
Ni(10wt%)Pd(10wt%)@CMK catalyst, Ni(NO3)2∙6H2O (0.310 g) and
Pd(NO3)2∙2H2O (0.156 g) were dissolved in distilled water (0.3 mL). The
mixed solution was dropped on CMK-3 powder (0.5 g) and infiltrated by
grinding the mixture in a mortar for several minutes under ambient
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a 30 mL
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polypropylene bottle and aged at 60 °C in an oven. After aging for 24 h,
the sample was cooled in an ambient atmosphere and transferred to an
alumina boat in a tube-type furnace. Finally, under a H2 flow of 0.2 L∙min-
1, the NiPd-incorporated CMK-3 powder was slowly heated to 350 °C at a
ramping rate of 2.7 °C∙min-1. The sample was thermally treated at 350 °C
for 4 h under the continuous H2 flow.
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Synthesis of Pd@CMK-3 and Ni@CMK-3 To prepare the
Pd(10wt%)/CMK-3 catalyst, aqueous Pd nitrate solution (1.74 M, 0.3 mL)
was dropped on CMK-3 powder (0.5 g) and infiltrated by grinding the
mixture in a mortar for several minutes under ambient condition until the
powder was homogeneously black. Then, the mixed powders were placed
in a polypropylene bottle and aged at 60 °C in an oven. After aging for 24
h, the sample was cooled in an ambient atmosphere and transferred to an
alumina boat in a tube-type furnace. Finally, under a H2 flow of 0.2 L∙min-
1, the Pd-incorporated CMK-3 powder was slowly heated to 350 °C at a
ramping rate of 2.7 °C∙min-1. The sample was thermally treated at 350 °C
for 4 h under the continuous H2 flow. For the preparation of the
Ni(10wt%)@CMK-3 nanocatalyst, all procedures were identical to those
used in the synthesis of Pd(10wt%)@CMK-3, except for the use of
aqueous Ni nitrate solution (6.3 M, 0.3 mL) and CMK-3 (1.0 g). For the
preparation of the Pd(20wt%)@CMK-3 nanocatalyst, all procedures were
identical to those used in the synthesis of Pd(10wt%)@CMK-3, except for
the use of aqueous Pd nitrate solution (3.92 M, 0.3 mL).
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Entry for the Table of Contents
COMMUNICATION
Ji Chan Park, Aram Kim, Sanha Jang,
Jung-Il Yang, Shin Wook Kang, Chan-
Woo Lee, Byung-Hyun Kim,* Kang Hyun
Park*
Page No. – Page No.
Facile synthesis of high performance
NiPd@CMK-3 nanocatalyst for mild
Suzuki-Miyaura coupling reactions
Text for Table of Contents
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