Nickel stabilized by triazole-functionalized carbon nanotubes as a novel reusable and efficient heterogeneous nanocatalyst for the Suzuki-Miyaura coupling reaction

Article abstract of DOI:10.1039/c6ra23004k

An interesting nanotube based nickel nanocatalyst was successfully prepared through "click" reaction of azide-functionalized nanotube with propargyl alcohol followed by immobilization of nickel nanoparticles. The as-prepared nanocatalysts behave as very efficient heterogeneous catalysts in the Suzuki-Miyaura cross coupling reaction in terms of activity and recyclability.

Full text of DOI:10.1039/c6ra23004k

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Nickel stabilized by triazole-functionalized carbon nanotubes as a
novel reusable and efficient heterogeneous nanocatalyst for the
Suzuki–Miyaura coupling reaction
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Abdol.R. Hajipour, a,b* Parisa Abolfathia
www.rsc.org/
An interesting nanotube based nickel nanocatalyst was successfully prepared through ‘‘click’’ reaction of
azide-functionalized nanotube with propargyl alcohol followed by immobilization of nickel nanoparticles. The
as-prepared nanocatalyst behave as very efficient heterogeneous catalysts in Suzuki-Miyaura cross coupling
reaction in terms of activity and recyclability.
walled carbon nanotubes (MWCNTs) have recently
attracted significant attention due to the high surface area,
high mechanical strength, ultra-light weight, high chemical
Introduction
Over the last few decades, carbon- carbon bond formation
reactions such as Suzuki, Heck, and Sonogashira and many
others are an important class of organic compounds due to
the prevalence of these moieties in many important
compounds of biological, pharmaceutical, polymer
industries and medicinal chemistry.1 Among the many
different coupling protocols, the palladium-phosphine
complexes is still one of the most frequently investigated
metals for such reactions.2-6 However, the use of palladium
catalysts has some major limitations including
contamination to products, moisture-sensitive nature, high
cost and toxicity.7 One promising solution to overcome this
issue is to employ available and cost-effective transition
metal than their palladium analogs.8 Recently, nickel
catalysis has attracted considerable attention as a viable
alternative to Pd catalyzed in cross-coupling reactions.9
These reactions are mostly performed under homogeneous
Ni catalytic systems which have some major limitations
such as using strong reducing agents, the lack of
recyclability, high catalyst loading (up to 10 mol%),
instability at high temperatures. Most of the issues
associated with homogenous catalyst can be solved by
immobilizing the catalyst in various heterogeneous
supports.10 Among the different catalyst supports, Multi-
and thermal stability 11-15
However, the difficulty for
.
functional groups to attach on it due to their strong
chemical stability behaviour and a lack of dispersibility in
organic solvents or in aqueous media is the major drawback
of pristine carbon nanotube for most applications. In order
to overcome this problem, two approaches for modifying
CNT have been developed, including covalent and
noncovalent
functionalization.
The
non-covalent
functionalisation involves van der Waals interaction, p–p
stacking interactions and the adsorption or wrapping of
various functional molecules around the nanotubes,16-19
and the covalent functionalisation based on attachment of
chemical of molecules onto the sp2 carbon atoms of the
CNTs.20 Many different covalent methods, such as acid
treatment, esterification, amidation, anionic coupling and
click coupling, have been developed for the covalent
modification of the sidewalls of CNT.21-24 In the past few
years, the copper(I)-catalyzed azide−alkyne cycloaddiꢀon
(CuAAC), known as the ‘‘click reaction’’, has received
unrivalled attention because of its high quantitative yield,
high tolerance of functional groups, compatibility with
water, mild and simple experimental conditions, high
chemoselectivity with no side products.25 Thus, the “click”
process has become an invaluable approach for the
efficient introduction of new functionalities onto CNTs.26- 29
As a part of our efforts to investigate on the application of
heterogeneous catalytic systems in cross-coupling
reaction,30–32 herein, we describe an interesting and facile
approach for the functionalization of multi-walled carbon
nanotubes using click reaction for the preparation of Ni
nanoparticles, as well as catalytic properties the latter for
performing Suzuki-Miyaura crosscoupling reaction.
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Result and Discussion
Preparation and characterization of the catalysts
A schematic illustration of the preparation strategy of the
MWCNTs-supported Nickel catalyst was shown in Scheme
1. First, pristine nanotubes were treated with strong acids,
in which hydroxyl moieties are created on nanotubes. In
the following step, the oxidized MWCNTs were further
reacted with 3- azidopropyltrimethoxysilane to introduce
an N3 group, which is subsequently reacted with propargyl
alcohol via click chemistry to furnish the modified
MWCNTs. Finally, the immobilization of Ni was carried out
by the reduction of NiCl2.6H2O in the presence of NaBH4 as
reducing agent, in H2O as the solvent system.
TBAB
(OMe)
Si
3
(OMe)
Si
3
+
NaN3
N3
Cl
Acetonitrile
Reflux, 48h
2
N3
OMe
Si
OH
OH
OH
O
EtOH
Reflux, 4h, N2
O
(OMe)
Si
3
+
N3
2
3
1
CuI
OH
DMF/THF
RT, 72 h
N
N
OH
Ni
OH
N
N
N
N
MeO
O
MeO
O
Si
Si
O
O
NiCl2 .6H2
NaBH4
O
5
4
Scheme 1 The nanocatalyst preparation
Fig.2 TEM images of nanocatalyst (a, b), SEM photographs
of Pure MWCNTs (c) and nanocatalyst (d)
solvent. The catalytic system was well characterized using
techniques including elemental analysis (EA), inductively
coupled plasma analysis (ICP), FT-IR, TEM, EDX, XRD and
SEM. FT-IR Spectroscopy was used to confirm the
modifications of the MWCNTs surface. As shown in Fig. 1b,
the absorption bond at 1092 cm-1 corresponds to the Si–O–
C stretching vibration and the peak at 2100 cm-1 is
attributed to N3 stretching, which demonstrates that the
azide groups have been successfully coupled to the surface
of the nanotube. As shown in Fig. 1c, the characteristic
vibration of azide completely was disappeared after the
click reaction between propargyl alcohol and N3-MWNTs. In
Fig. 1d, the intensity of the peaks is weaker than of
observed for the free ligand (Fig. 1c), supporting the
assumption that the ligand coordinates to the metal ion.
According to the results of elemental analysis, the loading
of the azide group on the carbon nantube surface was
determined to be 1.24 mmolg-1. The particle size,
morphology, and distribution of nickel nanoparticles
supported on MWCNTs were investigated using Scanning
electron microscopy (FE-SEM) and transmission electron
microscopy (TEM) imaging techniques (Fig. 2). As seen in
the typical TEM image of the catalyst, the NiNPs were of
spherical shape with relatively good monodispersity and
have average diameter ranging about 8 nm (Fig. 2a and 2b).
The information about the surface morphology of
functionalized carbon nanotube was also investigated by
scanning electron microscopy (SEM). As shown in Fig. 2d,
Fig.1 FT-IR spectra of 1 (a), 3 (b), 4 (c), 5 (d)
2 | J. Name., 2012, 00, 1-3
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the nanotubes are aggregated and have maintained their
nanotube nature after surface modification.
parameters such as bases, solvent, temperature conditions
and catalyst loading. In our first set of experiments, the
model reaction was studied in the presence of K2CO3 as
o
base and 20 mg of catalyst in different solvents at 100 C.
The results showed that the yield of product was enhanced
to 93% when 1, 4-dioxane was used as solvent.
Subsequently, we tested the impact of various bases on the
efficiency of this procedure because of its great influence in
this type of coupling reaction. On the basis of this study,
K3PO4 was chosen as the most effective and suitable base
for the reaction and the desired product was obtained in
97% yield after 6h (Table 1, entry 5). To obtain the proper
temperature for the cross-coupling, the model reaction was
also conducted at different temperatures and it was found
that reaction temperature plays a substantial role on this
transformation. As you can see in table 1, the improvement
in reaction results was achieved at 100 oC. Finally, we
investigated the effect of catalyst loading by employing
different amounts of catalyst. As you can see, the good
reaction time and higher yield were observed when the
reation was carried out with 20 mg of catalyst, while less
than this amount led to a decrease in the percentage yield
of the product. After optimization, Ni (0)/MWCNTs
catalyzed Suzuki reactions were examined with various
types of aryl halides (chlorides, bromides and iodides).
Results summarized in Table 2 show that aryl iodides and
aryl bromides were converted effectively to the desired
products with good yields in short reaction times. Also, the
less active chlorobenzene and its derivatives showed lower
yields and needed a longer time to obtain a moderate yield.
We also investigated the electronic effect on the yields and
reaction times of the reactions. Overall, the coupling
reaction of phenylboronic acid with electron withdrawing
aryl halides gave better conversions in shorter reaction
times. Steric factor of the procedure was surveyed using 2-
bromoacetophenone as hindered substituted aryls (Table 2,
Entry 6). It was observed that an increasing steric hindrance
of ortho substituents can cause a decrease in the reaction
conversion than those obtained with para-substituted ones.
Fig.3 SEM-EDX spectrum of the catalyst
As clearly observed, the EDS spectrum showed the elemental
composition after the grafting reaction, confirming the presence
of C, O, N, Si, Cl and Ni species in the catalyst (Fig. 3).
Meanwhile, the quantitative determination of the metal content
was determined by ICP analysis and was found to be 0.417
mmol g-1 for this catalyst. Fig. 4 presents the XRD-diffraction
patterns of the pristine MWCNTs and Ni (0) /MWCNTs. As
can be seen (Fig. 3a), the XRD pattern of MWCNT displays
two prominent peaks at around 2θ = 26 and 43o correspond
Fig.4 XRD pattern of pure MWCNTs (a), nanocatalyst (b)
to the (002) and (100) plane of hexagonal graphitic
structure on the mesoporous carbon. The observed
diffractions in sample Ni (0)/MWCNTs displays three
additional diffraction peaks at 44.5°, 51.6° and 76.9° (JCPDS,
no. 03–1051) belong to the diffraction peaks of Ni(111),
Ni(200) and Ni(220) reflections, respectively.
Catalytic tests
To evaluate the catalytic performance of the nanocatalyst
and to determine optimal conditions for Suzuki reaction,
phenylboronic acid and bromobenzene was selected as
model substrates and were examined under different
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a Reaction conditions: bromobenzene (1 mmol), phenylboronic acid
(1.2 mmol), base (2 mmol), amount of catalyst (20 mg), time (6h)
and solvent (5 ml). b Isolated yield. c Amount of catalyst used: 10 mg
d Amount of catalyst used: 15 mg, e Amount of catalyst used: 18 mg
Table 1 Effect of different parameters for the reaction
of bromobenzene with phenylboronic acida
Entry
1
Solvent
DMF
T(°C)
100
100
100
100
100
100
100
100
100
100
90
Base
K2CO3
K2CO3
K2CO3
K2CO3
K3PO4
KOH
Yieldb
76
Reusability and heterogeneity test
The level of recovery of the catalyst is highly preferable for
its industrial applications. In order to investigate this issue,
the reusability of Ni (0)/MWCNTs was examined by using
bromobenzene and phenylboronic acid as model
substrates. For this, after the completion of the reaction,
the catalytic system was separated from the reaction
mixture by centrifugation, washed thoroughly with water
and ethanol, dried and reused in subsequent reactions. As
shown in Figure 5, the described catalyst could be
recovered seven times without a noticeable loss of yield
and catalytic performance until the fifth reuse. However,
the yield of the reaction in the seventh run decreased to
62%. On the other hand, TEM image of used nanocatalyst
(after 7 runs) indicated the structure of Ni/ MWCNTs has no
significant change in comparison with fresh catalyst and the
catalyst preserves its structure Fig. S1, (ESI). The
comparison between the XRD measurements of the fresh
and the reused catalyst indicated that the metallic state of
nickel was kept during the reaction progress and Ni
nanoparticles do not removed from the MWCNTs surface
after the catalytic reaction Fig. S2, (ESI). The SEM images of
the seventh cycle of the catalyst are not considerably
different from the fresh catalyst, indicating that the
morphology of catalyst remained unchanged after seven
recoveries Fig.S3, (ESI). Also, the obtained ICP analysis from
the aqueous phases of reaction mixture after recycling
experiment showed only a low amount of Ni metal (0.094
ppm) was leaching out from the catalyst. These results
indicate that the attachment between nickel nanoparticles
and carbon nantube surface is sufficiently strong. To probe
this point that the nature of the active species originated
from the the supported nickel nanoparticles and not from
leached Ni, a hot-filtration test was conducted by coupling
of bromobenzene and phenylboronic acid. The reaction was
stopped and the catalyst was then removed from the
solution after 1 h (24%, analyzed by GC), the filtrate was
carried out further. No further progress in product yield
was detected even up to 6 h upon catalyst removal. The ICP
analysis only showed 0.04 ppm nickel in this solution,
indicating that metal leaching into the solution is negligible
and the catalyst was mainly heterogeneous in nature. So,
these results confirmed the high catalytic activity and good
stability of the catalytic system. To further evaluate the
efficiency of our catalyst, a comparison was made with the
reported heterogeneous Ni-catalysts in the Suzuki reactions
(Table 3). It can be clearly seen that our catalyst is superior
to others in terms of reaction condition, reaction time,
yield, recovery and reusability. The high catalytic
performance could be attributed to the high dispersion of
the NiNPs onto the outer surface of the nanotube.
2
Toluene
DMSO
90
3
85
4
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
93
5
97
6
64
7
NaHCO3
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
71
8
75c
83d
91e
86
9
10
11
12
80
71
Fig. 5 Reusability of the catalyst in the Suzuki-Miyaura
Experimental
All chemical reagents were purchased from Merck Chemical
1
Company and used without further purification. H-NMR
spectra were recorded on a Bruker 400 spectrometer using
deutrated CDCl3 as solvent and tetramethylsilane (TMS) as
internal standard. X-ray diffraction (XRD) powder patterns
were obtained using an X’PERT MPD, with Cu Kα radiation
(40 kV, 30 mA). Transmission electron microscopy (TEM)
images were obtained using a Philips CM10 microscope. FT-
IR spectroscopy (JASCO FT-IR 680-Plus spectrophotometer)
was employed for characterization of products. Also we
used Inductive coupled plasma Perkin Elmer Optima 7300
DV. Gas chromatography (GC) (BEIFIN 3420 gas
chromatograph equipped with a Varian CP SIL 5CB column:
30 m, 0.32 mm, 0.25 mm) was used for consideration of
reaction conversions and yields. Scanning electron
micrographs of the catalyst were taken on [FE-SEM,
HITACHI (S-4160)]. The acknowledgements come at the end
of an article after the conclusions and before the notes and
references.
4 | J. Name., 2012, 00, 1-3
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nitrogen atmosphere. After that, the obtained product was
washed thoroughly with water followed by acetone and
dried under vacuum at 80 ◦C.34
Synthesis of 3-azidopropyltrimethoxysilane
3-chloropropyltrimethoxysilane (5 mmol) is poured into a
solution
of
sodium
azide
(5
mmol)
and
tetrabutylammonium bromide (1 mmol) in dry acetonitrile
(75 mL) and the mixture is stirred under reflux for 48 h
under a nitrogen atmosphere. After the reaction, the
solvent was evaporated under reduced pressure. The crude
mixture was then dissolved in Et2O (30 mL) filtered and
washed twice with Et2O. The solvent was removed to
obtain 3-azidopropyltriethoxysilane (AzPTES).33
Click coupling between propargyl alcohol and N3-MWNTs
Azide functionalized MWCNTs (0.5 g) were dispersed in
DMF/THF (1:1, V/V) solution via ultrasonication for 10
minutes and propargyl alcohol (2 mmol) was added. Then
CuI (0.1 mmol) was added to the above solution. The
reaction mixture was stirred for 72 h at room temperature.
The completion of the reaction was checked by IR. The solid
particles was filtered and washed washed several times
with Et2O, H2O and then acetone and finally dried in
vacuum at 60 oC.35
Synthesis of azide-functionalized Multi-Walled Carbon
Nanotubes
The functionalization of MWCNTs surface was obtained via
oxidation with a mixture of concentrated sulfuric acid and
nitric acid. Briefly, 0.1 g of pristine MWCNTs was dispersed
in 50 mL of concentrated H2SO4/HNO3 (3:2 v/v) solution at
50 oC and stirred for 20 h. The solution was filtered, washed
several times with deionized water to reach pH=7 and dried
Preparation of Ni (0)/MWCNT
5 mL aqueous solution of NaBH4 (3 mmol) was dropwise to
an aqueous suspension containing 0.5 g of the modified
carbon nanotubes and 0.2 mmol of NiCl2.6H2O and
mechanically stirred at room temperature for 24 hours. The
resulting solid of Ni-MWCNT was separated from the
mixture by centrifugation, washed several times with water
and ethanol, respectively to remove unreacted NiCl2 and
dried under vacuum to obtain a black solid powder.
o
under vaccum at 100 C for 24 h. Afterward, the resulting
functionalized nanotubes were suspended in ethanol via
ultrasonication for 30 min and 3-azidopropyltriethoxysilane
was then added. The solution was refluxed for 4 h under
Table 2 Suzuki cross-coupling reaction of various aryl halides with phenylboronic acida
Entry
Ar–X
Product
Time(h)
Yieldb
TONc
1
6
97
116
Br
2
5
96
115
3
4
5
5
6
97
87
85
116
104
101
6.5
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6
10
63
75
7
8
9
4
4
4
3
9
7
9
96
93
93
98
84
88
78
115
111
111
117
100
105
93
10
11
12
13
a
Reaction conditions: aryl halide (1 mmol), phenylboronic acid (1.2 mmol), Base (2 mmol), Solvent (4 ml), catalyst (20 mg), 100 °C
b Isolated yield
c TON: Calculated using the 0.417 mmol/g Nickel (Obtained by ICP for Ni/MWCNT)
Table 3. Comparison of catalytic activity of the Ni (0)/MWCNT catalyst with literature precedents using Ni based
homogeneous and heterogeneous catalysts for Suzuki-Miyaura cross coupling reaction
Entry
Catalyst
Aryl halide
Br
conditions
Yield(%)ref
K3PO4, Dioxane
100 oC, 6 h
1
Ni (0)/MWCNT
97(This work)
K3PO4, Dioxane
100 oC, 5 h
2
3
Ni (0)/MWCNT
96(This work)
8336
octahedral nickel(II)
benzoylhydrazone complex
Toluene, K2CO3
Reflux, 8 h
Br
K3PO4, PPh3, LiBr,
dioxane,
Ni(II) mounted on
graphite (Ni/Cg)
4
5
6
8737
9538
9839
180-200 oC, 9h
NaOH, PCy3, dioxane,
120 oC, 12h
Magnetic Fe–Ni Alloy
Monodisperse Ni and
NiO nanoparticles
DMSO, 135 oC
6 | J. Name., 2012, 00, 1-3
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HPMC stabilized Ni
Nanoparticles
Ethylene Glycol, Cs2CO3,
100 oC, 20 h
7
9940
Z.–Q. Zhang, Y. –C. Liu, L. Liu, Angew. Chem. Int. Ed.,
2011, 50, 3904; (d) T. Hatakeyama, T. Hashimoto, K. K.
A. D. S. Kathriarachchi, T. Zenmyo, H. Seike, M.
Nakamura, Angew. Chem. Int. Ed., 2012, 51, 8834.
Conclusions
In summary, we have applied nickel nanoparticles
supported on modified multiwalled carbon nanotubes as
highly selective, economical and efficient heterogeneous
catalysts in the Suzuki cross-coupling reaction. The
corresponding Suzuki products were obtained in good
yields under relatively mild reaction conditions. Also, the
catalyst could be reused for seven consecutive runs without
a noticeable loss of its catalytic performance until the fifth
reuse.
9
(a) F. G. –Bobes, G. C. Fu, J. Am. Chem. Soc., 2006, 128,
5360; (b) P. Leowanawat, N. Zhang, A. –M. Resmerita, B.
M. Rosen, V. Percec, J. Org. Chem., 2011, 76, 9946; (c) C.
E. I. Knappke, A. J. von Wangelin, Angew. Chem. Int. Ed.,
2010, 49, 3568; (d) X. Hu, Chem. Sci., 2011,
2, 1867; (e)
S. L. Zultanski, G. C. Fu, J. Am. Chem. Soc., 2013, 135
,
624; (f) N. Zhang, D. J. Hoffman, N. Gutsche, J. Gupta, V.
Percec, J. Org. Chem., 2012, 77, 5956; (g)Y. –L. Xian, W.
–H. Guo, G. –Z. He, Q. Pan, X. Zhang, Angew. Chem. Int.
Ed., 2014, 53, 1.
Acknowledgements
We gratefully acknowledge the funding support received
for this project from the Isfahan University of Technology
(IUT), IR of Iran, and Isfahan Science and Technology Town
(ISTT), IR of Iran. Further financial support from the Center
of Excellence in Sensor and Green Chemistry Research (IUT)
is gratefully acknowledged.
10 (a) R. K. Sharma , A. Pandey, S. Gulati, Polyhedron, 2012,
45, 86; (b) R. K. Sharma, A. Pandey, S. Gulati, Appl.
Catal., A., 2012, 431, 33; (c) R. K. Sharma, S. Gulati, J.
Mol. Catal. A: Chem., 2012, 363, 291; (d) R. K. Sharma,
D. Rawat, Inorg. Chem. Commun., 2012, 17, 58; (e) R. K.
Sharma, C. Sharma, Catal. Commun., 2011, 12, 327; (f)
R. K. Sharma, C. Sharma, J. Mol. Catal. A Gen., 2010,
332, 53; (g) R. K. Sharma, S. Sharma, Dalton Trans.,
2014, 43, 1292; (h) R. K. Sharma, S. Sharma, G. Gaba,
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