In situ synthesis of carbon nanotube-encapsulated cobalt nanoparticles by a novel and simple chemical treatment process: Efficient and green catalysts for the Heck reaction

Article abstract of DOI:10.1039/c9nj00813f

In this study, we present a novel, fast and easy method for supporting metal nanoparticles onto the internal surface of multi-walled CNTs; these CNT-encapsulated nanoparticles as heterogeneous, efficient, inexpensive and green catalysts promote the Heck cross-coupling of a large library of functional substrates under mild and sustainable conditions. Remarkably, the introduced catalytic system could be reused for at least nine successive runs without a discernible decrease in its catalytic activity.

Full text of DOI:10.1039/c9nj00813f

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PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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In Situ Synthesis of Carbon Nanotube-Encapsulated
Cobalt Nanoparticles by a Novel and Simple Chemical
Treatment Processes: Efficient and Green Catalysts for
Heck Reaction
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Cite this: DOI: 10.1039/x0xx00000x
Abdol R. Hajipoura,b*, Zahra Khorsandia, Hossein Farrokhpour a *
In this work, we presented novel, fast and easy technique to follow for the synthesis of metal
nanoparticles supported into the internal surface of multiwall CNTs. This heterogeneous,
efficient, inexpensive and green catalyst promotes Heck cross-coupling of a large library of
functional substrates under mild and sustainable conditions efficiently. Amazingly, introduced
catalytic system could be reused for at least nine successive runs without a discernible
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
decrease
in
its
catalytic
activity.
CNTs and the transition states of chemical reactions
performed on them.28 Confinement of nanoparticles (NPs)
inside the channels of CNTs has been displayed to significantly
change the electrochemical properties of both CNTs and
encapsulated NPs.29
Introduction
The applications of metal oxide nanoparticles (NPs) in
catalysis, medicine1-3 and electronic devices4-9 as an
inexpensive and versatile materials is now of great interest.
Compared to the bulk, these nanomaterials have different
physical and chemical properties depending on their
morphology and size. Among their various properties, the
exceptionally high durability and activity, NPs have received
considerable attentions and their application as catalysts have
been investigated extensively. Among all candidates, cobalt-
based materials established as active and attractive catalyst
since it is readily available, non-toxic, low-cost and stable.10-16
However, current extensive reports about applications of
homogeneous catalysis appear to be less promising due to
metal contaminations, economical and environmental
problems. Therefore, using heterogeneous catalysts that can
overcome these limitations is required. Indeed, a large library
of inorganic and organic supports, including inorganic silica,
alumina and synthetic polystyrene has already been applied.17-
Construction of nanostructures where the NPs are integrated
into a conducting network with a quasi-1D dimension, has
great potential interest for applications in chemical industry.
Most of the filling methods reported currently are based on
the use of capillary forces to fill-up the CNTs channel.30-33
Proliferation of the selectivity of the filling, versus outer
surface decoration CNTs, were previously functionalized35-36
but in high temperature and complex thermal programs
conditions.37-39 Colin et al. reported a synthesizing cobalt-
based NPs with a homogeneous size (50 nm) which are well
selectively localized within the CNT channel. Formation of this
hybrid in their work were performed in extremely high
temperature conditions through multi-step procedure (at 900
°C for 2 h and 650 °C for a long time).40 Next in 2014, Huang et
al. found that the high charge over potential can be effectively
alleviated using CNTs-encapsulated NPs hybrid cathode
materials; they prepared these hybrid materials by a two-step,
harsh and time consuming synthetic approach, which included
wet impregnation and thermal annealing.41 In addition, some
other protocol have been developed such as including break
CNTs by Ag-catalyzed oxidation, ultrasonic treatment, and
stirring, followed by impregnation of iron catalysts, rhodium
and ruthenium catalytic materials.42
20
One of the attractive supporting materials to prepared
efficient heterogeneous catalyst is carbon nanotubes
(CNTs).21,22 It is expected that encapsulated NPs onto channel
of multiwalled carbon nanotubes (CNTs) could give rise to a
new family of hybrid materials with novel physical properties.
In the field of catalysis, the entrapped metal oxide
nanoparticles inside the carbon nanotubes channel was found
to exhibit strange catalytic behaviour due to the confinement
effect provided by the surrounding CNT walls.23-25 In carbon
nanotubes (CNTs), there is a difference in π-electron density of
bent graphene layers between the concave internal wall and
the convex external surface.26-27 Early theoretical studies
suggested a correlation between the electronic structure of
Considering to green chemistry and its aims of saving energy,
more convenient, mild and fast methods to synthesize
location-specific nanoparticle catalysts supported by CNTs was
quite challenging. Herein, development of liquid-phase filling
of CNT channel with cobalt NPs in mild reaction conditions
have been reported for the first time.
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This novel phosphine, palladium and ligand-free cobalt catalyst (Figure 1b). In Co-in-CNTs (I), synthesized via method I, the
was used as an efficient and recyclable heterogeneous catalyst cobalt-NPs were mostly inside the CNTs, with size same as
for Mizoroki-Heck reaction. Cobalt catalysts due to their diameter of CNT channel as can be seen in Figure 1c. From
economic and environmental merits prefer to traditional histogram, the nanoparticles size distribution are about 21 ± 5
palladium catalytic systems. However, to the best of our nm. The Co-in-CNTs (II) was distinguished as the best sample
knowledge, application of cobalt catalysts in coupling reaction due to good dispersing and he most effective catalyst; thus, its
are rare and a few studies have been reported.43-46
XPS analyses was applied for more characterization.
In continues of our research group experiences in using cobalt The TEM images and histogram nanoparticles of Co-out-CNTs
as high efficient and recyclable catalysts in cross-coupling was also illustrated in Figure 1d, as can be seen Co
reactions;47-50 herein, the cobalt-NPs encapsulated onto nanoparticles were directly supported on out surface of
carbon nanotube (Co-in-CNTs) and supported on out surface of multiwalled CNTs. The average Co particles sizes was found as
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carbon
nanotube
(Co-out-CNTs)
were
synthesized, 20 nm. The amount of cobalt and nanoparticles size for three
characterized and their catalytic activities was investigated and synthesized hybrids was collected in Table S2.
compared together.
Results and discussion
The multiwalled CNTs used in this work was shortened and
opened ends (Figure 1a). For preparation cobalt NPs
encapsulated within multiwalled CNTs, denoted as Co-in-CNTs,
after testing numerous probabilistic approaches, two different
methods was applied; in the first technique multiwalled CNTs,
cobalt salt and reduce agent was mixing in ultrasonic for 1 h
and then stirring for another 3 h at 30 ℃, just 0.5 wt% Co was
encapsulated within the channels of multiwalled CNTs.
Moreover, the Co-NPs was formed in relatively large size
which seems filled CNT channels (as can be seen in Figure 1c).
In the second technique, multiwalled CNTs, cobalt salt was
mixing in ultrasonic for 3 h at 30 ℃ and then was reduced;
surprisingly different results was achieved, more metal loading
(5 wt% Co), very smaller nanoparticles and more importantly
unblock CNT channels (Figure 1b). Cobalt NPs tagged on out
surface of multiwalled CNTs, denoted as Co-out-CNTs, was
prepared by depositing 10 wt% Co on the outer surface of the
multiwalled CNT channels through reported method (Figure
1b).39
Formation of cobalt NPs inside the CNTs channel is done faster
and in lower temperature than preparation reaction conditions
of Co-out-CNTs. One may thus conclude that the CNTs act as
nanoreactors to promote the nucleation and growth of cobalt
based NPs.51-53 It is worth noting that at the best of our
knowledge, it is the first report of introducing an easy, green
and mild technique for filling of CNTs with metal oxide NPs.
Morphology of the samples was characterized with a field
emission scanning electron microscope (FE-SEM) system and
compared to pure multiwalled CNTs images. As can be seen
the nanotubes are aggregated and has retained their nanotube
nature upon functionalization (Figure S1).
The surface-area data of the catalysts and pure multiwalled
CNTs are given in Table S1. They have high and the same BET
surface area. The nature of the Co NPs in Co-out-CNTs (Figure
S2) and which grown within the CNTs was checked by XRD
(Figure S3). The XRD pattern was refined by considering the
presence of two different phases, namely Co and Co2O3 (JCPDS
card 78-1970).54
The TEM images of prepared samples was given in Figure 1.
The end-opened carbon nanotubes was illustrated in Figure
1a. For Co-in-CNTs (II), synthesized via method II, an high
density of cobalt- NPs inside the CNT channel is observed with
smaller diameter compared to another one, the sized of Co
nanoparticles concluded from histogram was around 9 ± 5 nm
Figure 1. TEM images of (a) Opened end CNTs, (b) Co-in-CNTs
(I), (c) Co-in-CNTs, (d) (II) Co-out-CNTs
2 | J. Name., 2012, 00, 1-3
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The peaks corresponding to oxygen, carbon, nitrogen and aryl halides in progress of this reaction was examined. These
catalysts were compatible with a wide range of functional
groups such as nitro, methoxy, and carbonyl on the aryl
halides. Aryl halides substituted with electron-withdrawing
groups in comparison with the electron-donating substituents
exhibited better conversions. As can be seen in Table 2, for
both catalysts, aryl iodides were converted to the
corresponding Heck products in good yields and the reactivity
of the aryl bromides was lower. However, in using Co-out-
CNTs aryl chlorides were inactive, while they gave good yields
in present of Co-in-CNTs (II). The results obtained revealed
that the Co-in-CNTs (II) is extremely efficient catalyst for Heck
reaction. It perhaps related to this fact that the CNT wall inside
the channel was disordered and hydrophilic which allows the
easy filling of the tube with a liquid, thanks to the action of
capillary forces.
The nanoparticle-based catalytic systems on solid supports
makes the catalyst recyclable and reusable and reduces the
leaching of the particles. Moreover, catalyst recovering is an
essential property from economic, environmental, and
industrial points of view. Therefore, the reusability of catalysts
was checked and compared. The Mizoroki–Heck reaction of
iodobenzene (1.0 mmol) and methyl acrylate (1.2 mmol) was
cobalt are clearly observed in the XPS elemental survey (Figure
S4). As shown in the expanded spectrum, the peaks at 779.7
eV (2p3/2) and 795.57 eV (2p1/2) correspond to Co3O4. The
energy-dispersive X-ray analysis (EDX) results, obtained from
SEM analysis of Co-in-CNTs (II), clearly show the presence of
Co nanoparticles in the catalyst (Figure S5).
The catalytic performances of synthesized catalysts (Co-in-
CNTs (I), Co-in-CNTs (II) and Co-out-CNTs) was investigated and
compared in Heck coupling reactions (Table 1, entries 1, 2
versus entry 9). To reach this aims; reaction of iodobenzene
with methyl acrylate was selected as model reaction.
Surprisingly, Co-in-CNTs (II), in comparison with others (Co-
out-CNTs and Co-in-CNTs(I)), gave wonderful activity. These
results show important and unique features of the catalysis
within the nanotubes, it may be related to acting of
nanochannels of CNTs as highly efficient nanoreactors for the
heterogeneous Heck reaction. The less reactivity of Co-in-CNTs
(I) can be correlated to blocking of nanochannels of CNTs by
large size cobalt nanoparticles.
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The efficiency of ligand-free Co catalyst for the model reaction choice as model reaction. At the end of each reaction, catalysts
was separated, washed with ethanol and acetone, and reused.
Their reusability was shown in Table 3, the Co-out-CNTs was
reused five times without significant loss of activity. The
efficiency of Co-in-CNTs (II) was checked in nine runs, no major
losing in activity was observed.
However, to the best of our knowledge, this phosphine and
palladium catalyst is one of the rare presentation of highly
efficient and recyclable cobalt catalyst which can be used for
more than nine times without any considerable loss of its
catalytic activity. Our catalytic systems can be introduced as
efficient ligand-free catalyst for the Mizoroki–Heck reactions
and was compared with those reported for reaction of
iodobenzene and methyl acrylate in the literature, the results
are given in Table 4.
was also investigated and the result was added to the Table 1.
After establishing the Co-in-CNTs (II) as the most efficient
synthesized catalyst, different reaction conditions contain
various solvent, bases, catalyst amounts and temperature was
studied in model reaction. Results was listed in Table 1. The
optimized conditions was achieved as 20 mg catalyst, K2CO3 as
base, at 60℃ and in polyethylene glycol (PEG) as solvent.
Encouraged by our initial founding, generality and versatility of
two more efficient synthesized cobalt catalyst in Heck cross-
coupling reaction of aryl halides with methyl acrylate was
investigated. The results was summarized in Table 2.
The corresponding products were obtained in moderate to
good yields using both catalysts, the results was compared to
each other. The electronic and steric effects of substitution of
Table 1. Optimization reaction conditions on Heck reaction of iodobenzene with methyl acrylate in the presence of Co-in-CNTs (II) unless
noted. a
Entry
1c
Cat. (mg)
CoNPs-out-CNTs
Co-in-CNTs (I)
Base
K2CO3
Solvent
PEG
PEG
PEG
Temp. (ºC)
60
Yield b (%)
84
2c
3c
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K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
KOH
K3PO4
Na2CO3
NaHSO4
K2CO3
K2CO3
60
60
100
60
80
r.t
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60
60
60
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60
60
60
47
38
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97
95
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93
97
76
67
71
58
97
84
Co-NPs
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20
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20
20
20
20
40
Dimethylformamide (DMF)
DMF
DMF
DMF
ETOH:H2O
Dimethyl sulfoxide (DMSO)
PEG
PEG
PEG
PEG
PEG
PEG
PEG
10
aThe reaction was carried out with iodobenzene (1.0 mmol), with methyl acrylate (1.2 mmol), base (2 equiv.) solvent (2.0 mL) for 3 h.
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bGC yield; cFor 5 h
Table 2. Scope of Mizoroki–Heck cross coupling reaction a
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Co-out-CNTs
Co-in-CNTs (II)
Entry
X
R
Time (h)
Yield b (%)
Time (h)
Yieldb (%)
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I
I
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H
3-Br
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4-NO2
4-OMe
H
4-OMe
4-NH2
3-OMe
2-NO2
3-Br
4-OCH3
2-OMe
4-Cl
4-CN
4-CH3
4-NO2
H
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Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
4-OMe
4-NH2
-
-
a The reaction was carried out with aryl halide (1.0 mmol), methyl acrylate (1.2 mmol), K2CO3 (2.0 equiv.) in 2.0 mL PEG, 20 mg of catalyst (1 mol % of Co) at
60 ºC. b Isolated yield
Our technique, addition to advantages of heterogeneous carbon nanotube channel. Considering to challenging problem
catalysis such as easy separation, efficient recycling, to syntheses of site-specific metal nanoparticles in multiwalled
minimization of metal contamination, and low-cost, in CNTs in recent years; certainly, our presented technique can
comparison with current approaches required significantly less be a general facile and practical recipe to follow for the
time, lower temperatures, and greener media (low synthesis of metal nanoparticles supported into the internal
temperature, safe metal, and green solvent. It also gave surface of multiwalled CNTs. It is worth noting that such green
acceptable results without also tedious and difficult ligand and low temperature conditions to preparation cobalt NPs
supported process in contrast with other reported catalysts encapsulated in multiwalled CNT has never been reported up
that used carbon nanotubes as solid bed.
to now.
Our catalytic system in comparison with previous unrecyclable
palladium-free catalysts are readily prepared in few steps from
available starting materials. Furthermore, the nan size
characteristic catalysts provides a large available surface area
for better interaction with reactants in the media with using
low amount of the catalysts in short times in Heck reaction.
Table 3. Reusability of the catalyst
Entry
1
2
3
4
Yielda (Co-out-CNTs)
Yielda (Co-in-CNTs(II))
86
86
84
82
73
-
-
-
-
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97
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95
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91
88
85
5
6
Conclusions
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In summary, the present work allows synthesizing cobalt
nanoparticles which are well selectively localized within the
aIsolated yield
Table 4. Comparison of catalytic activities of our catalyst with literature examples for Heck reaction between iodobenzene and methyl acrylate
catalyzed with cobalt
Entry
Catalystref
Reaction conditions
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
Nano Co43
Co (2 mol%) in NMP at 130 ºC
Co (10 mol%) in NMP at 150 ºC
Co (2 mol%) in NMP at 140 ºC
Co (5 mol%) in DMF at 130 ºC
Co (3.5 mol %) in PEG at 80 ºC
Co (5 mol %) in toluene at 100 ºC
Co (1.1 mol %) in PEG at 80 ºC
Co (3.3 mol %) in H2O at 80 ºC
Co (0.17 mol %) in PEG at 60 ºC
Co (3.4 mol %) in PEG at 60 ºC
Co (1.7 mol %) in PEG at 60 ºC
14
24
16
12
5
3
1
0.75
78
56
85
98
85
87
88
95
47
84
97
44
Co/Al2O3
Nano Co45
Co-B46
Co–NHC@MWCNTs48
Co-IL@MWCNTs49
Co-MS@MNPs/Cs4753
MNPs@Boehmite-NH2-CoII NPs56
Co-in-CNTs(I)
9
10
11
5
5
3
Co-out-CNTs)
Co-in-CNTs(II)
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Moreover, it is one of the pioneer reports of ligand-free cobalt
catalyzed Heck cross-coupling with good yields in extremely
mild and sustainable reaction conditions (palladium and
copper-free, polyethylene glycol as solvent, 60 °C).
In addition, our catalytic system could be reused for nine
consecutive cycles without any marked loss of its activity. It is
anticipated that this will encourage theoretical and
experimental studies to further the fundamental
understanding of the host–guest interaction within metal
nanoparticles and nanotube systems
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Acknowledgements
We would like to thank to thank the Isfahan University of
Technology (IUT), IR Iran.
Notes and references
a
Department of Chemistry ,Isfahan University of Technology, Isfahan
84156, Islamic Republic of Iran
b
Department of Neuroscience, University of Wisconsin, Medical School,
Madison, WI53706-1532, USA.
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