Pd nanoparticles deposited on Isoniazid grafted multi walled carbon nanotubes: Synthesis, characterization and application for Suzuki reaction in aqueous media

Article abstract of DOI:10.1039/c6ra19934h

In this article a new heterogeneous nanocatalyst based on palladium supported on Isoniazide-functionalized multi-walled carbon nanotubes (MWCNTs) has been introduced. The synthetic process of preparation of the mentioned nanocatalyst (Isoniazide-MWCNTs/Pd

Full text of DOI:10.1039/c6ra19934h

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DOI: 10.1039/C6RA19934H
Pd nanoparticles deposited on Isoniazid grafted multi walled carbon
nanotubes: Synthesis, characterization and application for Suzuki reaction
in aqueous media
Mahsa Hajighorbani, Malak Hekmati*
Department of Pharmaceutical Chemistry, Faculty of Pharmaceutical Chemistry, Pharmaceutical Sciences
Branch, Islamic Azad University, Tehran, Iran.
Abstract. In this article the new heterogeneous nanocatalyst based on palladium supported
on Isoniazideꢀfunctionalized multiꢀwalled carbon nanotubes (MWCNTs) has been
introduced. The synthetic process of preparation of mentioned nanocatalyst (Isoniazideꢀ
MWCNTs/Pd) has been described. The formation of nanocatalyst was analyzed by FTIR,
Raman spectroscopy, XRD, EDS, TEM, SEM, WDX, ICP and CHN analysis. Additionally,
the (IsoniazideꢀMWCNTs/Pd) nanocatalyst was successfully employed in Suzuki cross
coupling reactions with wide variety of functionalized substrates. Design of experiments
indicates that the use of 0.2 mol% of Pd, K2CO3 as the base, and aqueous ethanol are the best
reaction conditions. Interestingly, the novel catalyst could be recovered and recycled four
times without any significant loss in its catalytic activity.
Keywords: Multiꢀwalled carbon nanotubes, Isoniazide, Palladium, Nanocatalyst, Suzuki
Introduction
Carbon nanotubes (CNTs) nanotubes have attracted considerable interests due to their
remarkable thermal conductivity,[1ꢀ3] mechanical,[4ꢀ6] and electrical properties.[6,7] In addition,
their excellent chemical and mechanical stability and large surface area make them an ideal
and potentially useful choice for applications in optics,[7,8] electronics,[9] catalysis,[10,11]
polymer composites,[12] and many others.[13]
The immobilization methods used to deposit palladium into heterogeneous solid beds have
been studied extensively, and diverse supports such as clay,[14] carbon nanofiber,[15]
montmorillonite,[16] magnetic mesoporous silica,[17] zeolite,[18] and metal oxides[19] have been
investigated. A current challenge in this area is the development of efficient immobilized
systems that could simultaneously fulfill the usual targets of achieving high TON values and
facilitate recovering and reuse as well as the need for obtaining Pdꢀfree final products,[20,21]
meeting the strict purity specifications for the pharmaceutical industry.[22,23]
Transition metalꢀcatalyzed protocols, especially palladium reactions, have become powerful
tools in chemical synthesis of many materials and compared with frequently used
palladium(II) complexes catalysts, palladium nanoparticles were found to exhibit remarkable
catalytic activities for Suzuki, Heck and Sonogashira crossꢀcoupling reactions,[24ꢀ32]
hydrogenation of many organic compounds,[33ꢀ35] oxidation of hydrocarbon,[36]
isomerization,[37] and decomposition of nitrogen monoxide,[38] which have been extensively
used in the synthesis of drugs and fine chemicals.[39ꢀ44]
*Address correspondence to Malak Hekmati, Department of Pharmaceutical Chemistry, Faculty of
Pharmaceutical Chemistry, Pharmaceutical Sciences Branch, (IAUPS), Tehran, Iran
Eꢀmail: mhekmatik@yahoo.com
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There have been a variety of reports describing the use of carbon materials for the
immobilization of Pd nanoparticles, the catalytic activity of Pd nanoparticles can be retained,
and the stability also can be improved to some extent.[45ꢀ47] In continuing our attempts toward
the extension of efficient and environmentally benign heterogeneous catalysts,[48] herein, we
will report a simple preparation of a novel IsoniazideꢀMWCNTs to deposition of palladium
nanoparticles (IsoniazideꢀMWCNTs/Pd) (Scheme 1). After characterization, Suzuki cross
coupling were selected to investigate its catalytic activity and recyclability.
Experimental
Materials
All the reagents were purchased from Aldrich and Merck used without any purification.
SOCl2, HCl, H2SO4, HNO3, H2O2 (30 wt%, aq), deionized water, NaH (80%), anhydrous
dimethylformamide (DMF), CaH2, and Isoniazide were obtained from Sigma Aldrich and
Merck.
Preparation of the Isoniazide-MWCNTs
Pristine MWCNTs (pꢀMWCNTs) were refluxed under stirring in the mixture of 1:3 (v/v)
◦
HNO3 and H2SO4 at 70 C for 30 h, which was followed by centrifugation and repeated
washings with DI water. The dried carboxylated MWCNTs (MCNTsꢀCOOH) were
suspended in a solution of thionyl chloride (excess) and DMF (1 mL). The suspension was
stirred at 65 ºC for 24 h. The solid was then separated by filtration and washed with
anhydrous THF (30 mL), and dried in vacuum to obtain MWCNTsꢀCOCl. The final product
was then subjected to functionalization with Isoniazide. Isoniazide (amineꢀtoꢀMWCNTs weight
ratio was 5:1) were mixed with 10 mL solution of DMF and TEA (1 mL) and then stirred for
5 minute. The obtained acyl chloride MWCNTs that dispersed in DMF (20 mL) by ultrasonic
bath for 15 min were subsequently, added to the suspension. The reaction mixture was kept at
120 °C for 2 days. The solid was then separated by filtration and washed with CH2Cl2 and
deionized water for several times and dried in vacuum. The concentration of drug on
MWCNTs is 0.18 mmol/g, which was determined by CHNS analysis.
Preparation of the Isoniazide-MWCNTs/Pd
The IsoniazideꢀMWCNTs (500 mg) were dispersed in CH3CN (30 mL) by ultrasonic bath for
30 min. Subsequently, a yellow solution of PdCl2 (30 mg) in 30 mL acetonitrile was added to
dispersion of IsoniazideꢀMWCNTs and the mixture was stirred for 10 hours at 25 ºC. Then,
the IsoniazideꢀMWCNTs/Pd(II) was separated by centrifugation and washed by CH3CN, H2O
and acetone respectively to remove the unattached substrates.
The reduction of IsoniazideꢀMWCNTs/Pd(II) by hydrazine hydrate was performed as
follows: 50 mg of IsoniazideꢀMWCNTs/Pd(II) was dispersed in 60 mL of water, and then
100 ꢁL of hydrazine hydrate (80%) was added. The pH of the mixture was adjusted to 10
with 25% ammonium hydroxide and the reaction was carried out at 95 °C for 2 h. The final
product IsoniazideꢀMWCNTs/Pd(0) was washed with water and dried in vacuum at 40 °C.
Scheme 1 depicted the synthetic procedure of IsoniazideꢀMWCNTs/Pd(0). The concentration
of palladium in the prepared catalyst was 1.8 wt% (0.19 mmol/g), which was determined by
ICPꢀAES and EDS.
General procedure for the Suzuki–Miyaura reaction
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Aryl halide (1 mmol), phenylboronic acid (1.1 mmol), K2CO3 (2 mmol), catalyst (15 mg that
contained 0.2 mol% Pd) and water/ethanol (1:1, 2 mL) were added to a 5 mL flask, and the
mixture was stirred mechanically at 60 ºC. The progresses of the reactions were monitored by
TLC. After completion of the reaction, the catalyst was separated from the reaction
mixture by centrifugation and the crude product was extracted using ethyl acetate. The pure
products were obtained by column chromatography on silica using the hexane and ethyl
acetate as eluent.
Results and discussion
The Isoniazideꢀfunctionalized MultiꢀWalled Carbon Nanotubes (IsoniazideꢀMWCNTs) was
conveniently synthesized from commercially available and cheap materials via reaction of
acylated carbon nanotubes with Isoniazide. Next, palladium nanoparticles were deposited onto
the surface of the IsoniazideꢀMWCNTs. The loading of Pd in the obtained material was
determined by inductively coupled plasma (ICP) analysis to be 0.19 mmol/g. The pathways
of IsoniazideꢀMWCNTsꢀPd fabrication are shown in Scheme 1.
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HNO3
H2SO4
Cl
OH
O
O
O
O
OH
SOCl2
Cl
Cl
HO
O
O
O
O
Cl
HO
TEA, DMF
reflux, 2 days
N
HN
H2N
N
N
HN
O
NH
O
NH
HN
H
N
H
O
N
HN
N
H
N
O
N
1. PdCl2
2. N2H4
Pd
N
N
Pd
Pd
Pd
HN
NH
Pd
NH
HN
H
O
HN
O
N
H
O
N
Pd
N
N
O
Pd
N
Pd
H
Pd
Pd
Pd
Scheme 1. Schematic diagram of IsoniazideꢀMWCNTsꢀPd fabrication.
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FTIR spectroscopy provided further confirmation that the surface of the MWCNTs was
modified by Isoniazide (Figure 1). Its shows the FTꢀIR spectra obtained for (a) MWCNTsꢀ
COOH, (b) Isoniazide, and (c) IsoniazideꢀMWCNTs. As it is seen in the curve a, the
absorption bands at 1705 cmꢀ1 was attributed to the CO stretching of the carboxylic acid
groups. In the curve b, the absorption band at ∼1400ꢀ1600 cmꢀ1 is attributed to the C=C
stretching of pyridine ring and the bands observed around 3411 cmꢀ1 and 3447 were assigned
to the NH stretching vibrations. In the curve c, the absorption band at 1673 cmꢀ1 is attributed
to the carbonyl stretching of the amide groups (ꢀCONHꢀ). Also, the bands observed around
2922 cmꢀ1 and 2858 were assigned to the bending vibration of CꢀH. The prominent IR bands
at ∼3180 and 3300 cmꢀ1 were ascribed to the NH stretching vibrations. These results
indicated that the Isoniazide was successfully bonded to the surface of MWCNTs through
amidation reaction.
Figure 1. FTIR spectra of (a) MWCNTsꢀCOOH, (b) Isoniazide, and (c) IsoniazideꢀMWCNTs
.
.
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Another method for assessment of functionalization reaction is Raman spectroscopy. Figure 2
shows the Raman spectra of the samples. Two main peaks in the Raman spectra were
appeared in the samples at 1338 and 1596 cmꢀ1 which are known as D and G bonds,
respectively. D band is related to disordered carbon atoms of MWCNTs corresponding to sp3
hybridized and G band shows the sp2ꢀhybridized of carbon atoms in the graphene sheets.
Area ratio of the D to G bands (ID/IG) can be used to assess the amount of defects in nano
particles structure. ID/IG ratio was increased for IsoniazideꢀMWCNTs (ID/IG=1.35) which
approves the successful conversion of MWCNTs to IsoniazideꢀMWCNTs. In the absence of
amorphous carbon, the increase of ID is related to increase of carbon containing sp3
hybridized and implies to successful functionalization reaction.
Fig. 2. Raman spectra of the (a) MWCNTs, and (b) IsoniazideꢀMWCNTs.
The morphology of the IsoniazideꢀMWCNTsꢀPd was characterized by field emission
scanning electron microscopy (FEꢀSEM) in Figures 3. The image of pristine MWCNTs
shows that the tube surfaces are clear and smooth (Figure 3a). It is observed that in the image
3b, the surface of CNTs uniformly coated, thus clearly indicative of Isoniazide units attached
to MWCNTs. In The image 3c, the decorated palladium nanoparticles on the Isoniazideꢀ
MWCNTs surface were distinguishable.
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Fig. 3. SEM images of (a) MWCNTs, (b) IsoniazideꢀMWCNTs, and (c) IsoniazideꢀMWCNTsꢀ
Pd
.
Energy dispersion Xꢀray spectroscopy (EDX) was recorded and shown in Figure 4. The
observed characteristic peak assigned to palladium metal in EDX spectrum, also evident the
successful formation of palladium nanoparticles. Other existing elements revealed by the
EDX analysis included carbon, oxygen, and nitrogen which confirmed that the Isoniazide
present on the surface.
Fig. 4. Energyꢀdispersive Xꢀray spectroscopy (EDS) of the IsoniazideꢀMWCNTsꢀPd
.
The wavelengthꢀdispersive Xꢀray spectroscopy (WDX)ꢀcoupled quantified FESEM mapping
of the sample was also investigated (Fig. 5). The wavelengthꢀdispersive Xꢀray spectroscopy
(WDX) can provide qualitative information about the distribution of different chemical
elements in the catalyst matrix. Looking at the compositional maps C and Pd, the presence of
Pd NPs with good dispersion is clearly distinguished in the composite.
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Fig. 5. FESEM image of IsoniazideꢀMWCNTsꢀPd and elemental maps of C and Pd atoms.
Transmission electron microscopy (TEM) investigations are carried out to observe the
morphology and distribution of palladium particles supported on IsoniazideꢀMWCNTs. The
existence of Pd nanoparticles, deposited on fꢀCNTs was clearly distinguishable as dark spots
in Fig. 6. From Fig. 6, we can see that Pd was well dispersed on the surface of Isoniazide
modified MWCNTs. The results indicated that Isoniazide play an important role to improve
the dispersibility of Pd. The mean diameter of Pd nanoparticles immobilized on fꢀCNTs was
found to be around ∼10 nm.
Fig. 6. TEM images of IsoniazideꢀMWCNTsꢀPd
.
Fig. 7 showed the Xꢀray diffraction spectroscopy (XRD) patterns of IsoniazideꢀMWCNTsꢀPd
.
As shown in Fig. 7, the wide diffraction peak at 2θ = 26° can be indexed to disorderedly
stacked hexagonal graphite structure [49]. The wellꢀdefined peaks around 39°, 47°, 68° and
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82° can be assigned to (111), (200), (220) and (311) crystal planes of Pd0 [49]. Thus the
XRD results indicate efficient immobilization of fcc structured Pd nanoparticles on fꢀCNTs.
Fig. 7. XRD pattern of IsoniazideꢀMWCNTsꢀPd
.
The XPS spectroscopic analysis of the heterogeneous catalyst is a quantitative technique to
indicate the electron properties of the species immobilized on the surface, such as oxidation
state, the electron environment and the binding of the core electron (E binding) of the metal.
Fig. 8 displays the Pd binding energy of IsoniazideꢀMWCNTsꢀPd. The study of the
IsoniazideꢀMWCNTsꢀPd at the Pd 3p level shows peaks at 532.3 and 553.6 eV for Pd 3p3/2,
which clearly indicates that the Pd nanoparticles are stable as metallic state in the
nanocomposite structure. In comparison to the standard binding energy of Pd0, with Pd 3p3/2
of about 532.4 eV and Pd 3p1/2 of about 560.2 eV, it can be concluded that the Pd peaks in the
IsoniazideꢀMWCNTsꢀPd shifted to lower binding energy than Pd0 standard binding energy.
The previous studies50,51 indicated that the position of Pd 3p peak is usually influenced by the
local chemical/physical environment around Pd species besides the formal oxidation state,
and shifts to lower binding energy when the charge density around it increases. Therefore, the
peaks at 553.6 and 532.3 could be due to Pd0 species bound directly to amino groups in the
IsoniazideꢀMWCNTs.
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Fig. 8. XPS spectra of IsoniazideꢀMWCNTsꢀPd for Pd 3p.
The prepared IsoniazideꢀMWCNTs supported heterogeneous Pdꢀcatalyst was then evaluated
in the CꢀC bond formation reaction of aryl halides with phenyl boronic acid as Suzukiꢀ
Miyaura coupling reaction. For optimization of the reaction, the Suzuki coupling reaction of
4ꢀmethylbromobenzene with phenyl boronic acid was chosen as a model for optimizing
reaction parameters such as the solvent, base, temperature and the amount of the catalyst.
Optimization conditions studies are summarized in Table 1. As expected, no target product
could be detected in the absence of the catalyst (Table 1, entry 11). However, addition of the
catalyst to the mixture has rapidly increased the synthesis of product in high yields. The
reactions were conducted using H2O/EtOH (1:1) as the best solvent. Among the bases
evaluated, K2CO3 was found to be the most effective. The effect of catalyst loading was
investigated employing several quantities of the catalyst ranging from 0.1 mol% to 0.3 mol%
(Table 1, entries 7,8 and 9). The best yield was obtained with 0.015 g (0.2 mol%) of the
catalyst (Table 1, entry 8). Also, the optimum temperature for the reaction was 60 °C (entry 8
versus entries 12, 13 and 14). In the case of 50 °C, the yield of the desired product was lower
than the one at 60 °C. However, when the temperature increased to 100 °C, the yield of the
desired product did not increase obviously.
Table 1. The optimization of reaction parameters for the Suzuki reaction of 4ꢀ
methylbromobenzene with phenylboronic acid.a
Br
various conditions
CH3
+
H3C
B(OH)2
Entry Pd (mol%)
Solvent
DMF
Base
T (°C) Time (h) Yield (%)b
1
2
3
4
5
0.2
0.2
0.2
0.2
0.2
K2CO3
K2CO3
K2CO3
K2CO3
80
60
60
90
60
3
4
2
5
2
75
60
75
60
65
Toluene
EtOH
H2O
EtOH/H2Oc NaOAc
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6
7
8
0.2
0.2
0.2
0.3
0.2
0.0
0.2
0.2
0.2
EtOH/H2Oc
Et3N
EtOH/H2Oc K2CO3
EtOH/H2Oc K2CO3
EtOH/H2Oc K2CO3
EtOH/H2Oc No base
EtOH/H2Oc K2CO3
EtOH/H2Oc K2CO3
EtOH/H2Oc K2CO3
EtOH/H2Oc K2CO3
90
60
60
60
60
60
25
50
100
4
2
1
80
75
98
96
10
0.0
60
80
98
9
1
10
11
12
13
14
12
12
6
2
1
aReaction conditions: 4ꢀmethylbromobenzene (1.0 mmol), phenylboronic acid (1.0 mmol), catalyst, base (2
mmol) and solvent (3 mL).
bIsolated yield.
c3 mL (1:1)
Several coupling reactions of various aryl halides (I, Br and Cl) with phenyl boronic acid were
evaluated using 0.2 mol% of IsoniazideꢀMWCNTsꢀPd under the optimized conditions and the
results presented in the Table 2. Phenyl iodides, bromides and chlorides all reacted efficiently
with phenylboronic acid (Table 2, entries 1ꢀ17). Aryl halides with electronꢀwithdrawing or
releasing groups reacted with phenylboronic acid to afford the corresponding products in high
yields. Notably, heteroaryl halides such as 2ꢀbromothiophene and 2ꢀiodothiophene with
phenylboronic acid gave the corresponding coupled products in 90% and 96% yields,
respectively (Table 2, entries 16 and 17). The coupling reaction of aryl chlorides with phenyl
boronic acid required extended reaction time than aryl iodides and bromides, producing the
desired products in moderate yield (Table 2, entries 3, 6, 9).
Table 2. Scope of the SuzukiꢀMiyaura reaction.a
X
Isoniazide-MWCNTs-Pd (14 mg)
H2O-EtOH, K2CO3, 60oC
+
R
B(OH)2
R
Entry RC6H4X
R
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
X
I
Br
Cl
I
Br
Cl
I
Br
Cl
I
Br
I
Br
I
Br
I
Br
Time (h) Yield (%)b
1
2
H
H
1.0
2.0
24
98
98
70
96
96
60
98
96
55
98
92
90
80
96
90
96
90
3
H
4
5
6
7
8
9
10
11
12
13
14
15
16
17
4ꢀCH3
4ꢀCH3
4ꢀCH3
4ꢀCOCH3
4ꢀCOCH3
4ꢀCOCH3
4ꢀCH3O
4ꢀCH3O
4ꢀNH2
4ꢀNH2
4ꢀOH
1.5
2.0
24
1.0
2.0
24
2.0
3.5
1.5
2.5
3.0
5.0
2.5
4.0
4ꢀOH
2ꢀThienyl
2ꢀThienyl
aReactions were carried out under aerobic conditions in 3 mL of H2O/EtOH (1:1), 1.0 mmol arylhalide,1.0 mmol
phenylboronic acid and 2 mmol K2CO3 in the presence of catalyst (0.015 g, 0.2 mol% Pd) at 60 ºC.
bIsolated yield
.
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It was found that the catalyst IsoniazideꢀMWCNTsꢀPd could be separated conveniently by
centrifugation and reused at least 4 times without significant lose in catalytic activity for the
Suzuki coupling reaction between phenylboronic acid and 4ꢀmethylbromobenzene in the
presence of K2CO3 (Fig. 9). After completion of the reaction, catalyst was separated by
centrifugation from the reaction mixture and washed several times with deionized water and
ethanol. Then, it was and dried in an oven at 50 °C and the recycled catalyst was saved for
the next reaction.
Fig. 9. Recyclability of catalyst in the SuzukiꢀMiyaura reaction (Reaction conditions: 4ꢀ
methylbromobenzene (1.0 mmol), phenylboronic acid (1.0 mmol), catalyst (0.015 g) , K2CO3
(2 mmol) and 3 mL of H2O/EtOH (1:1) at 60 ºC).
Leaching of palladium from the solid catalyst was examined employing a hot filtration test.
The reaction of 4ꢀmethylbromobenzene with phenylboronic acid in the presence Isoniazideꢀ
MWCNTsꢀPd catalyst at 60 ºC was performed and a solid precipitate was formed by adding 2
mL ethanol, which was collected by centrifugation. Then, the solidꢀfree filtrate was allowed
to continue to react under the same conditions for another 60 min. No increase in the amount
of the product was observed, which suggested that the leaching of Pd species from the solid
support is low and the prepared catalyst is stable. Moreover, the leaching of Pd into the
reaction solution after four runs was determined by ICP analysis to be 1.24 %, which
indicates the stability of the catalyst during the reaction. Also, the Pd loading in the reused
catalyst was determined by inductively coupled plasma (ICP) analysis to be 0.17 mmol/g.
This result indicated that the palladium catalyst is heterogeneous and remained on the support
at elevated temperatures during the reaction. Based on these evidences, a reaction mechanism
for Suzuki coupling with the prepared nanocatalyst was proposed (Scheme 2).
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Pd0
Pd0
Pd0
Pd0
Ar X
Oxidative addition
Pd0
Reductive elimination
Ar Ph
Pd0
Ph
Ar
X
Ar
Pd2+
Pd0
Pd0
Pd2+
Pd0
Pd0
Pd0
Pd0
Pd0
Pd0
Suzuki Reaction
Pd0
Pd0
Ph B(OH)2
Transmetalation
K2CO3
XB(OH)2
K2CO3
Scheme 2. Possible mechanism of Suzuki coupling reaction.
Conclusions
In this study, Isoniazide was successfully bonded on the surface of MWCNTs by reaction of
acylated carbon nanotubes with Isoniazide. Based on the results of IR, SEM, XRD, WDX,
ICP, TEM, Raman and CHN analysis confirmed the functionalization of MWCNTs with
Isoniazide. The prepared IsoniazideꢀMWCNTs were used to deposition of Pd NPs as novel
nanocatalyst. The catalyst showed high activity in Suzuki coupling reaction of aryl halides (X
= I, Br, Cl). The catalyst showed good stability and was recycled for several times without
significant loss in its catalytic activity. These advantages make the process highly valuable
from the synthetic and environmental points of view.
Acknowledgments. We are thankful to Payame Noor University and Pharmaceutical
Sciences Branch, (IAUPS), Tehran for partial support of this work.
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RSC Advances
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DOI: 10.1039/C6RA19934H
Graphical Abstract
Pd nanoparticles deposited on Isoniazid grafted multi walled carbon
nanotubes: Synthesis, characterization and application for Suzuki reaction
in aqueous media
Mahsa Hajighorbani, Malak Hekmati*
Pd
N
N
Pd
Pd
Pd
HN
O
NH
O
Pd
NH
HN
H
N
H
O
N
HN
Pd
N
N
O
Pd
N
Pd
H
Pd
Pd
Pd
X
H2O-EtOH,
K2CO3,
60 oC
R
B(OH)2
R
The prepared IsoniazideꢀMWCNTs were used to deposition of Pd NPs as novel nanocatalyst.
The catalyst showed high activity in Suzuki coupling reaction of aryl halides (X = I, Br, Cl).
16