Diaza crown-type macromocycle (kryptofix 22) functionalised carbon nanotube for efficient Ni2+ loading; A unique catalyst for cross-coupling reactions

Article abstract of DOI:10.1016/j.mcat.2020.111117

Raising the capability of supporting and suppressing the leaching possibility to a very insignificant level has still remained challenging for some class of transition metals, i.e. Ni²⁺. Here we present the covalent functionalisation of macrocyclic ligand, 4,13-diaza-18-crown-6 (kryptofix 22), on the surface of carbon nanotube (CNT), leading to a unique adsorptive capability for supporting Ni²⁺. This material was incorporated as a promising catalyst in coupling reactions including C[sbnd]C, CN, and CO[sbnd][sbnd] cross-coupling reactions. We demonstrate that the kryptofix 22 functionalisation on the surface of CNT has a key role in the enhancement of the adsorption capability Ni²⁺ and subsequent catalytic activity. We further prove that this ligand causes a significant boost in the recyclability of the reactions due to the extremely trivial Ni²⁺ leaching from the CNT's surface during the reactions.

Full text of DOI:10.1016/j.mcat.2020.111117

Molecular Catalysis 494 (2020) 111117
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
Diaza crown-type macromocycle (kryptofix 22) functionalised carbon
nanotube for efficient Ni2+ loading; A unique catalyst for cross-coupling
reactions
a
a,
b,
Michael Aalinejad , Nader Noroozi Pesyan *, Esmail Doustkhah *
a
Department of Organic Chemistry, Faculty of Chemistry, Urmia University, 57159, Urmia, Iran
International Center for Materials Nanoarchitechtonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
b
A R T I C L E I N F O
A B S T R A C T
Keywords:
Raising the capability of supporting and suppressing the leaching possibility to a very insignificant level has still
remained challenging for some class of transition metals, i.e. Ni . Here we present the covalent functionali-
2
+
Carbon nanotube
CeC coupling
eCN coupling
eCO coupling
Kryptofix 22
sation of macrocyclic ligand, 4,13-diaza-18-crown-6 (kryptofix 22), on the surface of carbon nanotube (CNT),
2+
leading to a unique adsorptive capability for supporting Ni . This material was incorporated as a promising
catalyst in coupling reactions including CeC, CN, and COee cross-coupling reactions. We demonstrate that the
kryptofix 22 functionalisation on the surface of CNT has a key role in the enhancement of the adsorption cap-
ability Ni2+ and subsequent catalytic activity. We further prove that this ligand causes a significant boost in the
4
,13-diaza-18-crown-6
2
+
recyclability of the reactions due to the extremely trivial Ni
reactions.
leaching from the CNT’s surface during the
1
. Introduction
even gaseous compounds [26–28]. Therefore, we used kryptofix 22 to
functionalise the surface of CNT to reinforce the surface loading cap-
ability. Kryptofix 22 is a highly potential macrocyclic compound for
incorporating in variety of applications due to its strong complexation
capability [29–31]. This macrocyclic compound can compose an orga-
nometallic complex with a broad number of metal ions by wrapping
and surrounding the metal with several nitrogen and oxygen atoms
[31]. Therefore, kryptofix 22 is expectable to have a high capacity in
loading metal ions and therefore, it is a promising candidate to be
functionalised on a heterogeneous surface to act as a ligand. The use of
Ni species as catalyst can be of great importance since Ni is a great
alternative to precious metals for coupling reactions from viewpoint of
cost-efficiency.
Nanoarchitecture of carbon-based materials toward a unique and
smart heterogeneous catalyst has acquired a significant attention in
recent years toward green chemical processes [1–4]. Heterogeneous
catalysts, among them, with transition metal basis as the frontiers of
green catalysis for chemical processes have granted many break-
throughs in the field [5–8], however, several transition metal ions like
2
+
Ni
are suffering from the high efficiency being efficiently loaded on
the surface with insignificant leaching [9–14]. Therefore, researches to
develop the textural ability of a heterogenous surface for a stronger
bonding to the metal ions are still ongoing. Among the candidates, pure
carbon-based materials can have only some weak bonding or interac-
tions with most metal ions and therefore, lead to an inefficient catalyst
due to low loading capacity and high leaching possibility [15–17].
However, bearing in mind that some of carbon materials (e.g. CNT)
have a high surface area, stability and potential in surface modification
In this work, we designed a catalyst by modifying the CNT surface
with kryptofix 22 to enhance the Ni2+ loading capacity [32], and
subsequent rise in the catalytic activity in the recyclability. This catalyst
3
was incorporated in the cross coupling of Ph SnCl with three different
[
18,19], it can easily convert to an exceptional material through
species including aromatic amine (CeN coupling), aromatic halides
(CeC coupling), and phenols (CeO coupling). We present a catalyst
high stability, surface area and recyclability for coupling reactions.
modifying the surface [16,20–25]. Therefore, we aimed to design a
catalyst based on CNT with subsequent modification toward a Ni2+
supported catalyst.
On the basis of previous reports, crown ether macrocyclic com-
pounds have an excellent capacity toward adsorption of metal ions,
⁎
Corresponding authors.
E-mail addresses: n.noroozi@urmia.ac.ir (N.N. Pesyan), Doustkhah.esmail@nims.go.jp (E. Doustkhah).
https://doi.org/10.1016/j.mcat.2020.111117
Received 20 April 2020; Received in revised form 8 June 2020; Accepted 6 July 2020
2468-8231/ © 2020 Elsevier B.V. All rights reserved.

M. Aalinejad, et al.
Molecular Catalysis 494 (2020) 111117
Scheme 1. Synthesis of CNT-Kryf/Ni.
2
−1
2. Result and discussion
Emmett-Teller (BET) plot CNT-Kryf/Ni has 1.210 m . g
as surface
area (Fig. 1b), which is significantly a high surface area. This ob-
servation also reveals that the surface area of CNT is not collapsed by
several modification and pretreatment steps in comparison with the
pristine types of CNT [33,34].
The loading amount of Ni in CNT-Kryf/Ni using ICP‐OES found to be
1.30 wt%. The morphology of CNT-Kryf/Ni according to the scanning
electron microscopy (SEM) reveals that the CNT parent morphology is
retained, as shown in Fig. 3. SEM-mapping and EDS demonstrated the
related elements (C, Si, N, O, and Ni) of CNT-Kryf/Ni dispersed
throughout the structure (Fig. 2).
2
.1. Catalyst synthesis and characterisation
Here, we modified CNT with a kryptofix 22 to obtain a unique
2
+
surface functionality for supporting Ni
load on a surface. For this, we pretreated the surface with HNO3/
which is, in turn, difficult to
SO
4
H
2
to generate plenty of hydroxyl and epoxide groups on the surface. The
generated hydroxyl groups contribute the surface of CNT to be well-
functionalised with CPTMS. Functionalisation of CPTMS decorates the
surface with alkyl chloride which subsequently can be incorporated for
post-functionalisation with kryptofix 22 (CNT-Kryf). Eventually, we
loaded CNT-Kryf with Ni2 to reach an organometallic based hetero-
geneous catalyst (CNT-Kryf/Ni). Scheme 1 presents a simplified step of
CNT-Kryf/Ni.
The Fourier transform infrared (FT‐IR) spectra were obtained at
various steps of catalyst synthesis (Fig. 4b). Accordingly, a peak at 1104
+
−
1
cm
isting peaks at 2761.42 and 2831.52 cm
stretching vibration peak of Kryptofix 22 and n‐propyl aliphatic chain.
could be attributed to the CeC bond vibration of CNT. The ex-
−1
could be due to the CHe
X-ray diffraction (XRD) pattern of CNT-Kryf/Ni is presented in
Fig. 1a. According to the XRD pattern, two characteristic peaks were
found at 25.8° and 43.2° which correspond to the (002) and (200)
−1
A band at 3438 cm
O‐H groups. Appearing some peaks around 1636–1676 cm
is assignable to the stretching vibration of the
−
1
after
planes. N
2
adsorption-desorption isotherm of CNT-Kryf/Ni was mea-
functionalisation of CNT with kryptofix 22 confirms the covalent
bonding of kryptofix 22 to the surface of CNT. Raman spectroscopy
sured and studied. According to the obtained isotherm and Brunauer-
Fig. 1. (a) Wide-angle XRD pattern and (b) N
2
adsorption-desorption isotherm of CNT-Kryf/Ni.
2

M. Aalinejad, et al.
Molecular Catalysis 494 (2020) 111117
Fig. 2. The EDX spectrum and elemental maps of C, O, Si, N and Ni of CNT-Kryf/Ni.
exhibits the hybridation of ratio of ordered and disordered carbons.
dimethylformamide, poly ethylene glycol, CH
rolidone and high yield was obtained by PEG (Fig. 5). The reaction of
aryl iodide with Ph SnCl in the presence of PEG as solvent, CNT-Kryf/
Ni as catalyst was efficiently proceeded at room temperature via a CeC
cross coupling. Then, the catalytic capability of other aryl halide deri-
2 2
Cl and N‐methyl pyr-
−
1
−1
Accordingly, D band at 1313 cm
and G band at 1604 cm
can be
attributed to the ordered and disordered carbon in CNT. Since the D
band has higher intensity and arises from defects of carbons, the
structure of carbon in CNT-Kryf/Ni is dominantly oxidised in the pre-
treatment step (Fig. 4a).
3
3
vatives with Ph SnCl was tested under the optimum conditions and the
results are summarised in Table 1.
Since the Stille CeC coupling reaction is an organometallic based
reaction, the mechanism can be also assumed as part of CeC coupling
reaction in which the metal species in the first step undergoes oxidative
2
2
.2. Catalytic tests
.2.1. eCC coupling reaction
In this step, CNT-Kryf/Ni as a heterogenous catalyst was tested and
3
addition to Ph SnCl and in the second step, the formed Ni complex 1
bears a transmetalation with Ph-Br to form complex 2. Eventually the
complex undergoes a reductive elimination and product 3 is obtained
and the Ni-L (L is indicative of CNT-Kryf) regenerates.
examined in different Stille coupling reactions (e.g. CeC, CN and
COee). Therefore, it was examined in the reaction of Ph SnCl with aryl
3
iodide to find out an efficient solvent and base, and an optimum tem-
perature to obtain a high yield (Scheme 2). Initially, we used different
amounts of catalyst to specify the optimum amount of catalyst. The
coupling reaction in the absence of catalyst did not have a tangible
progress, while in the presence of the CNT-Kryf/Ni (7 mg) the reaction
yielded a significant product (Scheme 2). Among different bases, such
as N‐methylmorpholine, Et
coupling reaction was K CO
this reaction showed us that the reaction can efficiently proceed at
room temperature and raisin the temperature is not an essential task.
This reaction was checked using several solvents including EtOAc,
2.2.2. eCN coupling reaction
CeN coupling is one of the most important reactions for synthesis of
vital intermediates of chemicals and pharmaceutical compounds
[32,35]. Therefore, after a successful test on the synthesis of different
biphenyl compounds over the catalysis of CNT-Kryf/Ni, the catalytic
activity of CNT-Kryf/Ni was examined in CeN cross coupling reaction
(Scheme 3). For optimizing the reaction conditions, aniline with
3
N and K
2 3
CO , the more effective base in this
. Seeking for an optimum temperature in
2
3
Ph
3
SnCl was selected as a model reaction in the presence of the catalyst.
N as base and PEG as
The experiments demonstrate that using Et
3
Fig. 3. a) Low and b) high magnification SEM images of CNT-Kryf/Ni.
3

M. Aalinejad, et al.
Molecular Catalysis 494 (2020) 111117
Fig. 4. a) The Raman spectrum of CNT-Kryf/Ni, b) FT‐IR spectra of CNTs (black), CNT-Kryf (red), and CNT-Kryf/Ni (blue). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article).
solvent at 95 °C results in CeN bond formation in a very high yield
(
Table 2, entry 2). Likewise, this reaction was also activated at higher
temperature like other many reactions [36]. The reaction of Ph SnCl
3
was further successfully applied for several other amines, as sum-
marised in Table 3, either the derivatives with electron‐withdrawing
groups or electron‐donating groups. Comparing the catalytic activity of
CNT-Kryf/Ni with CNT/Ni reveals that the presence of kryptofix 22 has
2
+
a key role in the improvement of the catalytic activity of Ni .This is
due to the high loading capacity of CNT-Kryf rather than pure CNT.
For discovering the role of kryptofix 22 in the catalytic activity of
Ni, the CeN coupling reaction was tested under the identical conditions
but with unmodified Ni supported CNT (CNT/Ni). The lower yield and
TON of the reaction when catalysed by CNT/Ni reveals the constructive
effect of the modification with kryptofix in the improvement of cata-
lytic activity (Scheme 3).
2.2.3. eCO coupling reaction
In this reaction, to gain the optimal reaction conditions of CeO
Fig. 5. Solvent influence on CeC coupling reaction of iodobenzene with
PhSnCl3 through the catalysis of CNT-Kryf/Ni.
cross coupling reaction, phenol with Ph
3
SnCl was tested under the
catalysis of CNT-Kryf/Ni. Therefore, we tested different solvents, bases,
temperatures and ratios of CNT-Kryf/Ni to reactants. Under the optimal
conditions, the reaction in the presence of Et N (as base) and PEG (as
3
solvent) at 95 °C for 24 h was found to be more efficient than other
evaluated conditions. The reactions of different phenol derivatives with
unmodified CNT, but pretreated with concentrated acid, and repeated
the reaction of phenol with Ph SnCl. We found that the reaction yield
3
significantly drops when the surface of CNT is not functionalised with
kryptofix 22 (CNT/Ni). This comparison reveals the excellence of
Ph
3
SnCl were studied also investigated and we found the same excellent
kryptofix 22 on enhancing the catalytic activity through the enhancing
results of this catalyst under the optimal conditions for other deriva-
2+
the Ni
loading capacity (Scheme 4). We also found that the TON of
2
+
tives of the reactant (Table 4). We also loaded the Ni directly on the
Scheme 2. CeC cross-coupling reaction of iodobenzene with Ph
3
SnCl under the catalysis of CNT Kryf/Ni or CNT/Ni under the identical conditions. (Reaction
conditions: 1 mmol iodobenzene, 0.5 mmol of Ph SnCl and 2 mmol of K
3
2
CO
3
in 2 mL of solvent).
4

M. Aalinejad, et al.
Molecular Catalysis 494 (2020) 111117
Table 1
Table 2
Coupling of aryl halides with Ph
temperature.
3
SnCl catalyzed by CNT-Kryf/Ni at room
Optimisation of parameters for CeN coupling reaction catalyzed by CNT-Kryf/
Ni.
Entrya
Solvent
Base
Temp (°C)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
9
PEG
PEG
PEG
Et
Et
3
N
95
95
95
Reflux
Reflux
r.t.
95
r.t.
24
11
10
20
20
22
20
16
14
24
–
3
N
N
N
N
N
N
N
N
97
90
50
55
85
65
60
82
–
Entry
1
Aryl halide
Producta
Yield (%)b
94
TON
93
Et
Et
Et
Et
Et
Et
Et
3
CH
2
Cl
2
3
3
3
3
3
3
EtOAC
–
DMF
PEG
PEG
PEG
2
3
95
90
95
90
65
95
1
0
K
2
CO
3
a
Reaction conditions: 1 mmol of aniline, 7 mg catalyst, 0.5 mmol of Ph
N in 2 ml of solvent.
Isolated yield.
3
SnCl
4
5
6
92
93
86
92
92
84
and 2 mmol of Et
3
b
Table 3
Coupling of amines with Ph
3
SnCl catalysed by CNT-Kryf/Ni at 95 °C.
Entry
1
Amine
Producta
Yield (%)b
TON
97
7
8
9
90
92
97
95
90
92
97
95
97
2
3
4
86
91
95
86
90
95
1
0
a
The products were characterised and identified by comparison of their
spectral and physical data with those of authentic samples.
b
Isolated yield.
5
6
70
78
70
76
a
The products were recognised and characterised by comparison of their
spectral and physical data with those of authentic samples.
b
Isolated yield.
compared to previously reported catalysts [38]. Table 5 reveals that the
catalysis of CNT-Kryf/Ni results in a superior or competitive activity
compared to the previously reported literatures in the identical reac-
tion. Eventually, the recyclability of the CNT-Kryf/Ni was further stu-
died for all three cross coupling reactions. As a result, recycling the
3
CNT-Kryf/Ni in the reaction of Ph SnCl with any of aryl halide, aniline
and phenol under the related optimum reaction conditions. As shown in
Fig. 6, the CNT-Kryf/Ni was reused for seven consecutive cycles without
a significant loss in the catalytic efficiencies. Based on ICP‐OES mea-
surements, the leaching of Ni from the catalyst’s matrix to the solution
after seven cycles was negligible (1.30 %).
Further, we carried out a hot filtration test for the synthesis of CeC
coupling reaction as a sample reaction with triphenyltin chloride and
aryl bromide in order to examine the leaching of nickel to the reaction
mixture and the heterogeneity of the catalyst. In this test, we filtered
the catalyst in 20th minutes of the reaction and allowed the reaction
Scheme 3. Schematic representation of CeC coupling mechanism through the
catalysis of CNT-Kryf/Ni.
reaction under the catalysis of CNT-Kryf/Ni is higher than that of CNT/
Ni). This observation also demonstrates the kryptofix 22-Ni2+ com-
plexation leads to an enhancement in the catalytic activity of the Ni2+
(
Schemes 4 and 5).
2.2.4. Recyclability and catalytic potential of CNT-Kryf/Ni
continue. Afterward, the we observed no change in the progress of the
Since the heterogeneity of the catalysts are important because of the
2+
reactions. This observation shows that there is no leached Ni
in the
recyclability and preventing the release of chemicals and toxic mate-
rials to the environment [37]. We finally compared the catalytic ac-
tivity of CNT-Kryf/Ni in all three reactions with previously reported
catalysts and realised that CNT-Kryf/Ni acts as a competitive catalyst
solution after filtration which is why the reaction progress was stopped
Fig. 7). We also observed the morphology and shape of recovered
CNT/Kryf/Ni and we realised that the catalyst has been unchanged
(
5

M. Aalinejad, et al.
Molecular Catalysis 494 (2020) 111117
Table 4
Coupling of phenol derivatives with Ph
3
SnCl catalysed by CNT-Kryf/Ni at 90 °C.
Producta
Entry
1
Phenol
Yield (%)b
TON
94
94
2
96
96
3
4
5
6
87
84
92
89
87
84
92
89
a
The products were identified and characterised by comparison of their spectral and physical data with those of authentic samples.
Isolated yield.
b
Scheme 4. CeN coupling reaction of aniline with Ph
3
SnCl in the presence of CNT-Kryf/Ni or CNT/Ni as catalyst under the identical conditions. (Reaction conditions:
N in 2 ml of solvent).
1
mmol aniline, 0.5 mmol of Ph SnCl and 2 mmol of Et
3
3
after seven cycles.
3. Experimental
3.1. Materials and apparatus
2.3. Conclusion
All chemicals were purchased from Sigma-Aldrich and Merck
We demonstrated that kryptofix 22 can be a unique ligand for Ni2+
companies. Nuclear magnetic resonance (NMR, 400 MHz) spectra were
recorded on BRUKER NMR-Spectrometer (AVANCE). The FT-IR spectra
were obtained with Nexus 670 FT-IR spectrometer. Thin layer chro-
matography (TLC) over silica gel SIL G/UV254 plates were used to
monitor the reactions progress. The amount of Ni loading was de-
loading on the surface of CNT through a simple post modification
process. Our proposed novel and retrievable catalyst (CNT-Kryf/Ni)
revealed a promising catalytic activity in the CeC, CN and COee cross-
coupling reactions. Furthermore, the catalyst was active for several
consecutive cycles without any leaching during the reaction. Our ob-
servations showed that this ligand on CNT has high potential to support
a vast majority of cations that are resistive to surface adsorption.
2
termined by ICP‐OES (VISTA-PRO). N adsorption–desorption isotherm
and BET plot were obtained by a Quantachrome Autosorb at 77 K. XRD
patterns were prepared using a Rigaku X‐ray diffractometer equipped
with a Cu radiation source. SEM observation and elemental SEM-EDS
analysis were carried out with FESEM-TESCAN MIRA3.
6

M. Aalinejad, et al.
Molecular Catalysis 494 (2020) 111117
Scheme 5. Cross coupling reaction of phenol with Ph
3
SnCl through the catalysis of CNT-Kryf/Ni and CNT/Ni under the identical conditions. (Reaction conditions: 1
3 3
mmol phenol, 0.5 mmol of Ph SnCl and 2 mmol of Et N in 2 ml of solvent).
Table 5
3.2. Synthesis of CNT-Kryf/Ni
Comparison of CeC, CO and CNee coupling reaction with CNT-Kryf/Ni and
other reported systems.
Multiwall CNT (2 g) was pretreated with concentrated H
2 4 3
SO /HNO
mixture (9.0 M for each acid) and sonicated at 70 °C for 3 h. The acid-
treated CNT (4.8 g) was further dispersed in in toluene/CPTMS (10 mL,
Reaction type Catalyst
Solvent
PEG
Temp. (°C) t (h) Yield (%) Ref.
C-C
C-O
C-N
Pd(II)La
Pd(II)Lꞌ
90
0.5
1
68
[39]
[40]
This
work
[41]
[42]
This
work
[43]
[42]
This
work
5
mmol) solution and stirred at reflux conditions for 48 h. Then, the
b
coupling
coupling
coupling
H
2
O
100
r.t.
100
97
obtained powder from the reaction was recovered by centrifugation and
washed with EtOH for three times. The obtained product from this step
(CNT-Cl, 1 g) was added to kryptofix 22 (1 g) and Et N (2 mL) in EtOH
3
(50 mL) and stirred under reflux for 24 h in a 100 ml round‐bottom
flask. Thus, the product (kryptofix 22/ MWCNTs) was filtered and
washed by dry ethanol and dried in vacuum oven at 70 °C. In the final
step, CNT-Kryf (3 g) was mixed with Ni(NO ) (1.5 g) in ethanol (50 ml)
3 2
was stirred under reflux for 20 h. The CNT-Kryf/Ni was separated by
filtration and washed with ethanol and dried in vacuum at 70 °C.
CNT-Kryf/Ni PEG
1.5
CuI, DMGc
Cu(OAc)
CNT-Kryf/Ni PEG
Dioxane 90
DMSO
16
20
18
86
86
94
2
120
95
Cu–L"d
Cu(OAc)
H
2
O
r.t.
r.t.
95
15
24
11
91
94
97
2
3
Et N
CNT-Kryf/Ni PEG
a
L: trans‐dichlorobis(triphenylphosphine).
Lꞌ: Benzothiazole‐based ligand.
N,N dimethylglycine.
b
c
3.3. General procedure for CeC, CO and CeeN couplings
d
L": N,N-bis(salicylidene)arylmethanediamin.
eFor CC coupling, aryl halide (1 mmol) was added to mixture of
triphenyltin chloride (Ph SnCl, 0.5 mmol), K CO (2 mmol) and CNT-
3 2 3
Kryf/Ni (7 mg), and PEG (5 ml) at room temperature and stirred. The
progress of the reaction was monitored by TLC. After reaction com-
pletion, the mixture was centrifuged to separate the catalyst. The re-
covered catalyst was then washed with water and ethanol for three
times for next cycles (3:2, 5 mL). The reaction residue was diluted with
chloroform and water, the extracted organic layer was dried with
MgSO and the solvent was vaporised to afford the product. The pro-
4
ducts were determined with gas chromatography a Shimadzu GC-2010
plus gas chromatograph equipped with a barrier ionisation discharge
(
BID) detector.
For CeO coupling, phenol (1 mmol), triphenyltin chloride (0.5
mmol) and Et N (2 mmol) in PEG (2 ml) were added to CNT-Kryf/Ni (7
3
mg) and the mixture was stirred at 95 °C, the progress of the reaction
being monitored using TLC. After reaction completion, the mixture was
centrifuged to separate the catalyst. The mixture was washed with
water and EtOAc (3 × 5 ml), and then the separated organic layer was
Fig. 6. Reusability of the CNT-Kryf/Ni CeC coupling (Purple), CeO (black),
and CNe coupling (blue) reactions. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article).
dried over MgSO
For CeN coupling, aniline (1 mmol), triphenyltin chloride (0.5
mmol) and Et N (2 mmol) in PEG (2 ml) was added CNT-Kryf/Ni (7 mg)
4
.
3
at 95 °C. The progress of the reaction was monitored by TLC. The cat-
alyst was separated by filtration and reused as such for the next ex-
periment. The mixture was washed with water and EtOAc (3 × 5 ml),
4
and then the separated organic layer was dried over MgSO and solvent
7

M. Aalinejad, et al.
Molecular Catalysis 494 (2020) 111117
Fig. 7. a) SEM image of CNT-Kryf/Ni recovered from CeC cross coupling reaction after seven consecutive cycles; b) Hot filtration test profile for CeC coupling
reaction.
was vaporised to provide the product.
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