Magnetization of graphene oxide nanosheets using nickel magnetic nanoparticles as a novel support for the fabrication of copper as a practical, selective, and reusable nanocatalyst in C-C and C-O coupling reactions

Article abstract of DOI:10.1039/d1ra03578a

Catalyst species are an important class of materials in chemistry, industry, medicine, and biotechnology. Moreover, waste recycling is an important process in green chemistry and is economically efficient. Herein, magnetic graphene oxide was synthesized using nickel magnetic nanoparticles and further applied as a novel support for the fabrication of a copper catalyst. The catalytic activity of supported copper on magnetic graphene oxide (Cu-ninhydrin@GO-Ni MNPs) was investigated as a selective, practical, and reusable nanocatalyst in the synthesis of diaryl ethers and biphenyls. Some of the obtained products were identified by NMR spectroscopy. This nanocatalyst has been characterized by atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM), wavelength dispersive X-ray spectroscopy (WDX), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) techniques. The results obtained from SEM shown that this catalyst has a nanosheet structure. Also, XRD and FT-IR analysis show that the structure of graphene oxide and nickel magnetic nanoparticles is stable during the modification of the nanoparticles and synthesis of the catalyst. The VSM curve of the catalyst shows that this catalyst can be recovered using an external magnet; therefore, it can be reused several times without a significant loss of its catalytic efficiency. The heterogeneity and stability of this nanocatalyst during organic reactions was confirmed by the hot filtration test and AAS technique.

Full text of DOI:10.1039/d1ra03578a

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Magnetization of graphene oxide nanosheets using
nickel magnetic nanoparticles as a novel support
for the fabrication of copper as a practical,
selective, and reusable nanocatalyst in C–C and
C–O coupling reactions†
Cite this: RSC Adv., 2021, 11, 25867
b
Parisa Moradia and Maryam Hajjami
*
Catalyst species are an important class of materials in chemistry, industry, medicine, and biotechnology.
Moreover, waste recycling is an important process in green chemistry and is economically efficient.
Herein, magnetic graphene oxide was synthesized using nickel magnetic nanoparticles and further
applied as a novel support for the fabrication of a copper catalyst. The catalytic activity of supported
copper on magnetic graphene oxide (Cu–ninhydrin@GO–Ni MNPs) was investigated as a selective,
practical, and reusable nanocatalyst in the synthesis of diaryl ethers and biphenyls. Some of the obtained
products were identified by NMR spectroscopy. This nanocatalyst has been characterized by atomic
absorption spectroscopy (AAS), scanning electron microscopy (SEM), wavelength dispersive X-ray
spectroscopy (WDX), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD),
thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and vibrating sample
magnetometer (VSM) techniques. The results obtained from SEM shown that this catalyst has
a nanosheet structure. Also, XRD and FT-IR analysis show that the structure of graphene oxide and
nickel magnetic nanoparticles is stable during the modification of the nanoparticles and synthesis of the
catalyst. The VSM curve of the catalyst shows that this catalyst can be recovered using an external
magnet; therefore, it can be reused several times without a significant loss of its catalytic efficiency. The
heterogeneity and stability of this nanocatalyst during organic reactions was confirmed by the hot
filtration test and AAS technique.
Received 7th May 2021
Accepted 8th July 2021
DOI: 10.1039/d1ra03578a
rsc.li/rsc-advances
mineral materials,4,22 metal–organic frameworks (MOFs),23 and
biochar nanoparticles24 have been used for the fabrication of
1 Introduction
metallic catalysts. Among them, graphene oxide nanosheets
with a high surface area including high density of carbonyl,
hydroxyl, epoxide, and carboxylic acid groups on its surface
were used as a support for the stabilization of metallic ions.25
Therefore, graphene oxide can employed as an ideal support for
the functionalization and hybridization of other nanomaterials
such as metal catalysts for chemical reactions.5 It can also be
used as a suitable support for various catalytically active species
involving high catalytic activity. However, the recycling of the
supported catalyst on the graphene oxide surface is difficult due
to its nanosize.26,27 In this context, magnetic nanoparticles have
emerged an interesting support in green and sustainable
chemistry.28–30 However, magnetic nanoparticles have a high
tendency for aggregation due to the high surface energy and
attraction of magnetic cores, which lead to a loss of their cata-
lytic activities.5,27 A combination of heterogeneous nano-
catalysts with magnetic nanoparticles could be a viable solution
for the abovementioned problems.31 These composite systems
One of the principles of green chemistry is the use of stable and
recyclable catalysts that reduce costs and waste.1–3 Therefore,
many efforts have been made recently to introduce these
heterogeneous catalysts. For example, the stabilization of
metallic nanoparticles on solid materials is an effective way for
the synthesis of heterogeneous catalysts.4–6 However, the stabi-
lization of the catalytically active species on heterogeneous
substrates leads to a decrease in the catalytic activity.7,8 There-
fore, nanostructures with a high surface area are used to revive
the catalytic activity of stabilized species.9–11 For example,
magnetic nanoparticles,11–13 polymers,14 carbon nanotubes,15
ionic liquids,16,17 mesoporous materials,18–20 graphene oxide,5,21
aDepartment of Chemistry, Faculty of Science, Ilam University, P. O. Box 69315516,
Ilam, Iran
bDepartment of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University,
6517838683, Hamedan, Iran. E-mail: mhajjami@yahoo.com; m.hajjami@basu.ac.ir
† Electronic supplementary information (ESI) available. See DOI:
10.1039/d1ra03578a
have
a
high surface area of the nanocatalysts and
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simultaneously prevent the aggregation of magnetic cores
effectively.31 One of the important composite systems is
magnetic graphene oxide, which is composed of graphene oxide
and magnetic nanoparticles.32,33 Magnetic graphene oxide has
the advantages of both graphene oxide nanosheets (large
specic surface area) and magnetic nanomaterials (magneti-
cally recoverable by an external magnet). Therefore, magnetic
GO has been reported by the combination of graphene oxide
with Fe2O3,34 Fe3O4,35,36 ZnFe2O4,37 CoFe2O4,38 Co,39 and so on.
However, magnetic nickel nanoparticles have been rarely used
as the magnetic core for the magnetization of GO nanosheets.40
It is worthy to note that C–C or C–O coupling reactions are
usually performed in the presence of palladium-containing
catalysts,18,31 which are very expensive. Meanwhile, Cu-
containing catalysts are of interest because of their non-
toxicity and cost-effective preparation methods.4 Therefore,
herein, we have synthesized magnetic nickel-graphene oxide
nanosheets as a support to fabricate the copper catalyst (Cu–
ninhydrin@GO–Ni MNPs), and subsequently its catalytic
application was studied in the C–C and C–O coupling reactions
for the synthesis of diaryl ethers and biphenyls.
Scheme 1 Synthesis of nickel magnetic nanoparticles (Ni MNPs).
stirred for 24 h at room temperature. Finally, GO–Ni MNPs were
separated by an external magnet and washed with deionized
water. The synthesized GO–Ni MNPs were dried at 50 ꢀC
(Scheme 2).
2.4 Immobilization of Cu on GO–Ni MNPs for the
preparation of Cu–ninhydrin@GO–Ni MNPs
At rst, amino-functionalized magnetic GO nanosheets
(NH2@GO–Ni MNPs) were prepared according to a recently re-
ported procedure.64 Then, NH2@GO–Ni MNPs (1 g) were
dispersed in ethanol (25 mL) for 30 min. Aerwards, 3 mmol of
ninhydrin was added to the mixture and reuxed for 24 h under
N2 atmosphere. The formed powder (ninhydrin@GO–Ni MNPs)
was separated via an external magnet using ethanol washing
and dried at 50 ꢀC. Ninhydrin@GO–Ni MNPs (1 g) was dispersed
in ethanol (25 mL). Then, Cu(NO3)2$9H2O (2 mmol) was added
and reuxed for 24 h under N2 atmosphere. The nal product
(Cu–ninhydrin@GO–Ni MNPs) was washed with ethanol and
obtained via magnetic decantation. The obtained catalyst was
2 Experimental
2.1. Synthesis of graphene oxide
Graphene oxide was prepared from graphite powders using
modied Hummers' method.21 In this regard, concentrated
sulfuric acid (23 mL) was added slowly to a mixture of graphite
powder (1 g) and NaNO3 (0.5 g), and it was then stirred in an ice
bath for 15 min. Then, potassium permanganate (3 g) was
slowly added to the stirred mixture and again allowed to stir for
1.5 h at 0 ꢀC. Then, the mixture was stirred for 2 h at 35 ꢀC. Aer
this, deionized water (46 mL) was slowly added under stirring
ꢀ
dried at 50 C (Scheme 3).
2.5 General procedure for the synthesis of di-aryl ethers
ꢀ
and the solution temperature was stirred at 98 C for 30 min.
A mixture of phenols (1 mmol), aryl halide (1 mmol), KOH (5
mmol), and Cu–ninhydrin@GO–Ni MNPs (30 mg, 2.12 mol%)
in DMSO was stirred at 130 ꢀC and the progress of the reaction
was monitored by TLC. At the end of the reaction, the mixture
was cooled down and the catalyst was separated by an external
magnet and washed with ethyl acetate. The remaining reaction
mixture was extracted with H2O and ethyl acetate. The organic
phase was dried using anhydrous Na2SO4 (1.5 g) and the organic
solvent was evaporated to achieve the pure product.
Finally, deionized water (140 mL) and hydrogen peroxide (30%,
10 mL) were added. The resulting solution was washed with HCl
(10%) and deionized water. Then, graphite oxide was obtained
by centrifugation several times. Finally, GO nanosheets were
exfoliated by ultrasound for 30 min.
2.2 Synthesis of magnetic nickel nanoparticles (Ni MNPs)
A mixture of NiCl2$6H2O (0.5 g) and ethylene glycol (30 mL) was
stirred and heated up to 60 ꢀC. Then, hydrazine hydrate (1.4 mL)
was added dropwise. Aerwards, NaOH solution (1 M, 3.6 mL)
was added to the mixture, in which a black suspension was
formed aer 5 min. This suspension was stirred for 1 h at 60 ꢀC.
Finally, magnetic nickel nanoparticles (Ni MNPs) were sepa-
rated with the assistance of an external magnet and washed
with deionized water several times. The obtained Ni MNPs were
dried at room temperature (Scheme 1).
2.6 General procedure for the synthesis of biphenyls
A mixture of aryl halide (1 mmol), Na2CO3 (3 mmol, 0.318 g),
1 mmol of phenylboronic acid (PhB(OH)2), and Cu–ninhy-
drin@GO–Ni MNPs (30 mg, 2.12 mol%) was stirred in H2O at
80 ꢀC and the progress of the reaction was monitored by TLC. At
the end of the reaction, the mixture was cooled down, the
2.3 Synthesis of magnetic graphene oxide using nickel
magnetic nanoparticles (GO–Ni MNPs)
Graphene oxide (0.3 g) was dispersed in deionized water (50 mL)
for 20 min. Then, Ni MNPs (0.1 g) were added to the mixture and
Scheme
2 Synthesis of magnetic graphene oxide using nickel
again dispersed for another 20 min. Aerwards, the mixture was magnetic nanoparticles (GO–Ni MNPs).
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Scheme 3 Immobilization of copper on magnetic graphene oxide for the preparation of Cu–ninhydrin@GO–Ni MNPs.
2.7 Selected NMR data
[1,10-Biphenyl]-4-carbonitrile. 1H NMR (400 MHz, CDCl3): dH
¼ 7.85–7.67 (m, 4H), 7.65–7.62 (d, J ¼ 8 Hz, 2H), 7.58–7.53 (t, J ¼
8 Hz, 2H), 7.51–7.45 (t, J ¼ 8 Hz, 1H) ppm.
4-Chloro-1,10-biphenyl. 1H NMR (400 MHz, CDCl3): dH
¼
7.59–7.56 (m, 2H), 7.54–7.51 (m, 2H), 7.49–7.45 (m, 2H), 7.44–
7.42 (m, 2H), 7.40–7.37 (m, 1H) ppm.
4-Nitro-1,10-biphenyl. 1H NMR (400 MHz, CDCl3): dH ¼ 8.34–
8.29 (d, J ¼ 8 Hz, 2H), 7.77–7.73 (d, J ¼ 12 Hz, 2H), 7.66–7.62 (d, J
¼ 8 Hz, 2H), 7.54–7.44 (m, 3H) ppm.
1
Diphenyl ether. H NMR (400 MHz, CDCl3): dH ¼ 7.16–7.11
(m, 4H), 6.94–6.89 (t, J ¼ 12 Hz, 4H), 6.87–6.84 (d, J ¼ 12 Hz,
2H) ppm.
1
1-Methyl-4-phenoxybenzene. H NMR (400 MHz, CDCl3): dH
¼ 7.42–7.33 (m, 2H), 6.29–6.24 (t, J ¼ 8 Hz, 1H), 7.21–7.12 (q, J ¼
12 Hz, 2H), 7.08–7.03 (t, J ¼ 8 Hz, 2H), 7.00–6.86 (m, 2H), 2.39 (s,
3H) ppm.
1-Nitro-4-phenoxybenzene. 1H NMR (400 MHz, CDCl3): dH
¼
8.15–7.92 (m, 2H), 7.43–7.35 (t, J ¼ 8 Hz, 2H), 7.22–7.10 (m, 2H),
Fig. 1 SEM image of Cu–ninhydrin@GO–Ni MNPs.
7.08–7.04 (t, J ¼ 8 Hz, 2H), 6.88–6.85 (t, J ¼ 12 Hz, 1H) ppm.
catalyst was separated by an external magnet and washed with
ethyl acetate. The remaining reaction mixture was extracted 3 Results and discussion
with H2O and ethyl acetate. The organic phase was dried using
anhydrous Na2SO4 (1.5 g). Then, the organic solvents were
evaporated and pure biphenyl derivatives were obtained.
3.1 Catalyst characterization
Aer the preparation of Cu–ninhydrin@GO–Ni MNPs, this
catalyst was characterized by SEM, WDX, EDS, FT-IR, TGA, XRD,
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Fig. 2 EDX spectrum of Cu–ninhydrin@GO–Ni MNPs.
AAS, and VSM techniques. The SEM image of Cu–ninhy- in Fig. 3, all the elements are homogeneously distributed within
drin@GO–Ni MNPs is shown in Fig. 1. As shown in Fig. 1, this the structure of this catalyst.
catalyst was synthesized as nanometer sheets with a thickness
of less than 10 nm.
Moreover, the exact amount of copper that was loaded on the
modied GO–Ni MNPs was calculated by AAS analysis.
The elemental composition of Cu–ninhydrin@GO–Ni MNPs According to the obtained results from AAS analysis, there is
was qualitatively determined using EDS analysis (Fig. 2). As 0.71 ꢁ 10ꢂ3 mol of copper per gram of Cu–ninhydrin@GO–Ni.
expected according to Scheme 3, the obtained results from EDS
The FT-IR spectra for Ni magnetic nanoparticles (Ni MNPs),
show that this catalyst is composed of a combination of C, O, graphene oxide nanosheets (GO), magnetic graphene oxide by
Si, N, Ni, and Cu elements. Ni MNPs (GO–Ni MNPs), and Cu–ninhydrin@GO–Ni MNPs are
Also, the obtained results from EDS were conrmed by WDX shown in Fig. 4 and Table 1. The surface of GO is covered by
analysis. The elemental composition distribution of this cata- a high density of hydroxyl groups, which appears as a strong
lyst was investigated using WDX qualitative analysis. As shown band above 3000 cmꢂ1 (Table 1, entry 1) in the FT-IR
Fig. 3 Elemental mapping of (a) carbon, (b) oxygen, (c) silica, (d) nitrogen, (e) nickel, and (f) copper for Cu–ninhydrin@GO–Ni MNPs.
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Fig. 5 Magnetization curves for (a) Ni MNPs and (b) Cu–ninhy-
drin@GO–Ni MNPs.
and Si–O–C.43 The bands at 1250, 1205, and 1050–1125 cmꢂ1
(Table 1, entries 8–10) are attributed to the vibration of C–O–C,
epoxide, and C–O groups attached to GO, respectively.43,45,46 The
peak at 1199 cmꢂ1 is attributed to the stretching vibration of the
carboxyl C–O bonds.46 The vibration of the C]N bonds is
present at 1625 cmꢂ1 in the FT-IR spectrum of the catalyst
47
(Table 1, entry 12).
Fig. 4 FT-IR spectra of (a) Ni magnetic nanoparticles (Ni MNPs), (b)
graphene oxide nanosheets (GO), (c) magnetic graphene oxide by Ni
MNPs (GO–Ni MNPs), and (d) Cu–ninhydrin@GO–Ni MNPs.
The magnetic properties of Ni MNPs and Cu–ninhy-
drin@GO–Ni MNPs were studied by a VSM magnetometer at
room temperature (Fig. 5). As shown in Fig. 5, Ni MNPs have
a good magnetization value of about 45.71 emu gꢂ1. As ex-
pected, Cu–ninhydrin@GO–Ni MNPs showed a lower magnetic
value than the Ni MNPs, which was found to 10.06 emu gꢂ1. The
decrease in the magnetic value of the catalyst compared to that
of the Ni MNPs is due to the shielding of the magnetic property
by GO and the organic moieties on its surface. The VSM curve of
Cu–ninhydrin@GO–Ni MNPs conrmed that this catalyst can
be isolated by an external magnet.
Table 1 FT-IR characteristic absorptions
Entry
Functional group
Absorption (cmꢂ1
)
Reference
1
2
3
4
5
6
7
8
O–H bonds
C–OH bonds
C–H bonds
>3000
1224
878, 2958
1624
1714
462, 800
1040, 1082
1250
1205
1050–1125
1199
41
42
24
43
44
43
43
45
43
46
46
47
C]C bonds
C]O bonds
Si–O–Si bonds
Si–O–C bonds
C–O–C bonds
Epoxides
Alkoxy C–O bonds
Carboxyl C–O
C]N bonds
In order to indicate the stabilization of the organic groups on
the surface of GO–Ni MNPs, thermogravimetric analysis (TGA)
of Cu–ninhydrin@GO–Ni MNPs was performed over air ow
9
10
11
12
1625
spectrum.41 The characteristic stretching peak for C–OH groups
(Table 1, entry 2) on the surface of GO emerged at 1224 cmꢂ1
.
42
The bending and stretching vibration of the C–H bonds are
present at 878 and 2958 cmꢂ1 in the FT-IR spectra (Table 1,
entry 3).24 The bands at 1624 cmꢂ1 and 1714 cmꢂ1 correspond to
the vibration of the C]C bonds in the skeletal network of GO
(Table 1, entry 4) and C]O (Table 1, entry 5) bonds, respec-
tively.43,44 The bands at about 462, 800, 1040, and 1082 cmꢂ1
(Table 1, entries 6 and 7) correspond to the vibrations of Si–O–Si
Fig. 6 TGA curve of Cu–ninhydrin@GO–Ni MNPs.
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and a heating ramp of 10 ꢀC minꢂ1 in the temperature range of and (2 2 0), respectively. These reections conrm a face-
30–800 ꢀC. The TGA curve of Cu–ninhydrin@GO–Ni MNPs is centered cubic structure (FCC) of Ni MNPs.53–55 Also, these
indicated in Fig. 6, which indicates the various mass losses from reections and peak intensity broadening conrms the
this catalyst at different temperatures. The rst is indicated at formation of Ni nanoparticles.56,57 The strong peaks
low temperatures between 25–100 ꢀC, which corresponds to 4% conrmed that Ni MNPs have a pure and highly crystalline
weight loss. This mass loss is attributed to the evaporation of structure.56 The normal XRD pattern of graphene oxide
adsorbed solvents.48,49 The second weight loss, which is about
18%, is observed between 100 and 250 ꢀC, which is attributed to
the decomposition of thermally less stable and labile oxygen-
Table 2 Investigation of the optimal conditions for the coupling
containing functional groups (hydroxyl, epoxy, and carboxylic
reaction of iodobenzene with PhB(OH)2 in the presence of Cu–nin-
hydrin@GO–Ni MNPs
acid).21,50 The third weight loss at about 300 C corresponds to
ꢀ
the more stable oxygen-containing functionalities and the bulk
pyrolysis of the carbon skeleton.51,52 The fourth weight loss,
which shows a major decrease in the mass of about 31% in the
temperature range of 250–450 ꢀC, is attributed to the decom-
position of supported organic moieties and the copper complex
on the surface if GO–Ni MNPs,21,31 which can be possibly related
to the strong chemical interaction between GO–Ni MNPs and
the organic groups.
Amount
of catalyst
Entry (mg)
Temperature Time Yield
Solvent
Base
(ꢀC)
(min) (%)
1
2
3
4
5
6
7
—
20
30
40
30
30
30
H2O
H2O
H2O
H2O
PEG
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
80
80
80
80
80
80
80
360
120
50
40
50
N.R.
93
97
96
18
The structure of the synthesized materials was character-
ized by XRD using a PW1730 instrument from Philips
DMSO
1,4-
50
50
40
Trace
Dioxane
DMF
H2O
H2O
H2O
H2O
H2O
˚
company having CuKa (l ¼ 1.540598 A) radiation at 40 kV and
8
9
10
11
12
13
30
30
30
30
30
30
Na2CO3
KOH
NaOCH3 80
Et3N
K2CO3
Na2CO3
80
80
50
50
50
50
50
50
52
48
36
58
79
43
30 mA with 2q ¼ 9–90ꢀ. The normal XRD patterns of Ni MNPs,
GO, GO–Ni MNPs, and Cu–ninhydrin@GO–Ni MNPs are
shown in Fig. 7. The normal XRD pattern of Ni MNPs reveals
three characteristic peaks at 2q values of 44.55ꢀ, 52.25ꢀ, and
76.10ꢀ, which correspond to the Miller indices (1 1 1), (2 0 0),
80
80
60
Fig. 7 Normal XRD patterns of Ni MNPs, GO, GO–Ni MNPs, and Cu–ninhydrin@GO–Ni MNPs.
Scheme 4 Carbon–carbon coupling reaction of PhB(OH)2 with aryl halides in the presence of Cu–ninhydrin@GO–Ni MNPs.
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nanosheets reveals characteristic peak at the 2q value of
10.70ꢀ (0 0 2).21 Also, the several weak peaks of 2q, which are
observed at 2q ¼ 20–30ꢀ correspond to the labile oxygen-
containing functional groups.58 These less thermally stable
oxygen-containing functionalities were observed in the TGA
3.2 Catalytic application of Cu–ninhydrin@GO–Ni MNPs
Aer the characterization of Cu–ninhydrin@GO–Ni MNPs, its
application was investigated in the Suzuki coupling reaction.
The C–C coupling reaction in the presence of Cu–ninhy-
drin@GO–Ni MNPs is shown in Scheme 4. The optimum
conditions were obtained in the cross coupling of phenyl-
boronic acid (PhB(OH)2) with iodobenzene as the model reac-
tion under various parameters and different conditions (Table
2). At rst, the amount of the catalyst has been optimized in an
aqueous solution of Na2CO3 at 80 ꢀC. For this reason, the model
reaction was examined in the absence of the catalyst (Table 2,
entry 1), in which no products were obtained even until 6 h. The
model reaction was repeated for consecutive runs in the pres-
ence of 20, 30, and 40 mg of the catalyst. As shown in Table 2
(entries 2–4), increasing the amount of the catalyst led to an
increase in the reaction rate and product yields. However,
increasing the amount of the catalyst from 30 mg to 40 mg does
ꢀ
curve as a weight loss between 100 and 250 C. There are no
peaks corresponding to Ni MNPs in the XRD spectrum of GO.
The XRD pattern of the GO–Ni MNPs is combined of both
diffractions from Ni MNPs and graphene oxide nanosheets,
which reveals the successful preparation of GO–Ni MNPs.
Also, all the reections and their positions have remained in
the XRD pattern of the Cu–ninhydrin@GO–Ni MNPs aer the
modication of the nanoparticles and the fabrication of the
catalyst, which conrms the crystalline stability of Ni MNPs
and graphene oxide nanosheets during the preparation of the
catalyst.
Table 3 Catalytic C–C coupling reaction of aryl halides with PhB(OH)2 in the presence of Cu–ninhydrin@GO–Ni MNPs
Entry
1
Aryl halide
Product
Time (min)
50
Yield (%)
97
TON
45.7
TOF (hꢂ1
54.90
)
2
3
120
135
96
91
45.3
42.9
22.64
19.08
4
5
6
115
95
93
95
92
43.7
44.8
43.4
22.89
28.30
10.01
260
7
8
60
65
89
97
42.0
45.7
42.0
42.23
9
140
94
44.3
19.00
10
11
240
420
90
93
42.4
43.7
10.61
6.27
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not signicantly affect the reaction. Therefore, 30 mg (including presence of Cu–ninhydrin@GO–Ni MNPs. In order to extend the
2.12 mol% of copper) of Cu–ninhydrin@GO–Ni MNPs has been scope of this procedure, the coupling of a sample of aryl halide
chosen as the best amount of the catalyst (Table 2, entry 3). containing fused ring compounds with PhB(OH)2 (Table 3, entry
Then, the model reaction was examined in different solvents in 9) was investigated in the presence of Cu–ninhydrin@GO–Ni
the presence of a constant amount of the catalyst (30 mg, MNPs, which has a high TOF value and excellent yield of the
2.12 mol%) under the same conditions (Table 2, entries 4–8). obtained products were observed in carbon–carbon coupling
Among several solvents such as H2O, DMSO, 1,4-dioxane, DMF, reactions.
and PEG, the best results were obtained in water as the solvent.
The selectivity of Cu–ninhydrin@GO–Ni MNPs was
Aerwards, the effect of several organic and inorganic bases was conrmed for the coupling of 1-bromo-4-chlorobenzene with
studied in the model reaction in the presence of 30 mg of the PhB(OH)2 (Table 3, entry 5). As mentioned, the cross-coupling of
catalyst in water as the solvent. In these studies, sodium aryl bromides is faster than that of aryl chlorides. Therefore, the
carbonate was showed the best results in term of the reaction chloro functional group was not coupled with PhB(OH)2 and
time and yield. Finally, the effect of temperature was studied in pure 4-chloro-1,10-biphenyl was formed as the only product
the model reaction. As shown in Table 2 (entries 3 and 13), (Scheme 5).
decreasing the temperature from 80 to 60 ꢀC led to a reduction
The catalytic cycle for the cross-coupling reaction of aryl
in the yield of the products from 97% to 43% for a constant time halides with PhB(OH)2 in the presence of Cu–ninhydrin@GO–
of the reaction. Based on the abovementioned studies, the Ni MNPs is outlined in Scheme 6.31,64 In the rst step, oxidative
optimal conditions for carbon–carbon coupling reaction were addition gives intermediate I. Then, the reaction of the base
obtained in water at 80 ꢀC in the presence of 30 mg (2.12 mol%) with PhB(OH)2 as a Lewis acid produces PhB(OH)3, which, aer
of Cu–ninhydrin@GO–Ni MNPs using sodium carbonate (Table a transmetallation step, gives intermediate II. Finally, the
2, entry 3).
products were formed aer the reduction elimination step and
Aer obtaining the optimal conditions for the coupling the catalyst was regenerated simultaneously to continue the
reaction of iodobenzene with PhB(OH)2, the scope of the cata-
lytic activity of Cu–ninhydrin@GO–Ni MNPs was extended to
the coupling of other aryl halides with PhB(OH)2. Therefore,
various aryl iodides, aryl bromides, and aryl chlorides were
investigated in the cross-coupling reaction with PhB(OH)2 in the
presence of Cu–ninhydrin@GO–Ni MNPs (Table 3). All the
products were isolated in excellent yields and high TOF values
in short reaction times. However, the coupling of aryl iodide
with PhB(OH)2 is easier and faster than aryl chloride or aryl
bromide in the presence of this catalyst. For example, the
highest TOF value was obtained for iodobenzene. In the other
hand, the lowest TOF value was obtained for chlorobenzene.
Therefore, the order of reactivity of aryl halides is aryl iodides >
aryl bromides > aryl chlorides. Also, the effect of the electronic
nature of the functional groups on the aromatic ring of the aryl
halides was investigated by various electron-donating or
electron-withdrawing groups. For example, the highest TOF Scheme 6 The catalytic cycle for the cross-coupling reaction of aryl
halides with PhB(OH)2 in the presence of Cu–ninhydrin@GO–Ni
MNPs.
value or a shorter reaction time was obtained for the cross
coupling of 4-bromophenol with PhB(OH)2 in the presence of
Cu–ninhydrin@GO–Ni MNPs. Meanwhile, the lowest TOF value
or a longer reaction time was obtained for the cross coupling of
4-nitrobromobenzene with PhB(OH)2 in the presence of Cu–
ninhydrin@GO–Ni MNPs. As shown in Table 3, the reactivity of
para-functionalized bromobenzenes can be sorted as 4-OH > H
> 4-NO2. Therefore, aryl halides bearing an electron-donating
group are faster than aryl halides bearing an electron-
withdrawing group in the C–C coupling reaction in the
presence of Cu–ninhydrin@GO–Ni MNPs.
Scheme 7 C–O coupling reaction of phenol with aryl halides in the
Scheme 5 Selectivity in C–C coupling reactions in the presence of Cu–ninhydrin@GO–Ni MNPs.
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Table 4 Investigation of the optimal conditions for the synthesis of diphenyl ether in the presence of Cu–ninhydrin@GO–Ni MNPs
Amount of catalyst
(mg)
Temperature
(ꢀC)
Yield
(%)
Entry
Solvent
Base
Time (min)
1
2
3
4
5
6
7
8
—
30
20
35
30
30
30
30
30
30
30
30
30
DMSO
DMSO
DMSO
DMSO
PEG
KOH
KOH
KOH
KOH
KOH
KOH
KOH
Na2CO3
NaHCO3
Et3N
NaOCH3
NaOH
KOH
130
130
130
130
130
130
Reux
130
130
130
130
130
100
300
120
160
105
120
120
120
120
120
120
120
120
120
N.R.
98
90
93
48
72
35
20
27
55
31
74
67
DMF
H2O
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
9
10
11
12
13
Table 5 C–O coupling reaction for the synthesis of di-aryl ethers catalyzed by Cu–ninhydrin@GO–Ni MNPs
Entry
Aryl halide
Product
Time (h)
Yield (%)
TON
46.2
TOF (hꢂ1
23.11
)
1
2
98
2
3
4
2
8
91
95
88
42.9
44.8
41.5
21.46
5.60
3.77
11
5
6
3
9
94
92
44.3
43.4
14.77
4.82
7
8
7
93
86
43.9
40.6
6.27
3.38
12
9
24
90
42.4
1.77
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catalytic cycle. According to this mechanism, non-polar solvents couple aryl iodides or aryl bromides compared to aryl chlorides
are not capable of solvation of polar intermediates and also the (Table 5, entry 7). In order to extend the scope of this procedure,
base is insoluble in these solvents. Therefore, non-polar the coupling of 1-bromonaphthalene with phenol (Table 5,
solvents are not suitable for the Suzuki reaction. But the polar entry 9) was examined in the presence of Cu–ninhydrin@GO–Ni
solvents have the ability to dissolve the base and can also the MNPs, in which the corresponding ether was obtained in
dissolve the polar intermediates. Therefore, the polar solvents excellent yield.
lead to an increase in the Suzuki reaction rate. Protic solvents
A cyclic mechanism for the synthesis of diaryl ethers in the
provide better conditions for the Suzuki reaction than aprotic presence of Cu–ninhydrin@GO–Ni MNPs is outlined in Scheme
solvents. The obtained results in Table 2 show a good agree- 8. The cyclic mechanism includes the oxidative addition,
ment with the mechanism of C–C coupling reaction.
transmetallation, and reduction elimination steps, which lead
The catalytic activity of Cu–ninhydrin@GO–Ni MNPs was to the formation of diaryl ethers from the coupling of aryl
also investigated for the synthesis of di-aryl ethers through the halides with phenol and the regeneration of the catalyst to
C–O coupling reaction of aryl halides with phenol (Scheme 7). continue the catalytic cycle.59
The optimal conditions for the synthesis of ethers were ob-
The natural heterogeneity of Cu–ninhydrin@GO–Ni MNPs
tained in the coupling reaction of iodobenzene with phenol as was studied by the hot ltration test and AAS analysis.60 Initially,
the model reaction (Table 4) under different conditions. At rst, the coupling reaction of 4-nitrobromobenzene with PhB(OH)2
different amounts of the catalyst were investigated. As shown in in the presence of this catalyst was performed under the opti-
Table 4 (entry 1), the model reaction did not occur in the mized conditions. This reaction was stopped aer 130 min, in
absence of the catalyst even until 6 h. Meanwhile, the reaction which 61% of 4-nitro-1,10-biphenyl was obtained as the product
rate and product yields were increased with an increase in the at this time. In order to evaluate the copper leaching, the exact
amount of the catalyst. Eventually, 30 mg (2.12 mol%) of the amount of copper was calculated in the ltered solution by AAS
catalyst was selected as the optimal amount of Cu–ninhy- aer removing the catalyst by an external magnet. In this
drin@GO–Ni MNPs (Table 4, entry 2). In the second step, the analysis, the concentration of copper in the ltered solution was
model reaction was tested in several solvents in the presence of found to be 0.000003 mol Lꢂ1. Therefore, copper leaching is
a constant amount of the catalyst (30 mg, 2.12 mol%). There- negligible during the reaction. This means that Cu–ninhy-
fore, polar protic solvents (such as PEG and H2O) and polar drin@GO–Ni MNPs is heterogeneous in nature and the
aprotic solvents (such as DMSO and DMF) were examined in the described reactions take place under heterogeneous conditions.
model reaction. As shown in Table 4, acceptable results were To conrm these results, the reaction of 4-nitrobromobenzene
obtained in aprotic solvents. Finally, DMSO was selected as the with PhB(OH)2 was repeated. Halfway through the completion
optimal solvent. In continuation, the effect of the several inor- of the reaction, the reaction stopped and the reaction solution
ganic and organic bases was examined in the model reaction in was allowed to proceed in the absence of catalyst. In this stage,
DMSO and in the presence of 30 mg of the catalyst. Alkali 65% of 4-nitro-1,10-biphenyl was obtained as the product. These
hydroxides as the base gives better results than other bases in experiments conrm that the leaching of copper did not occur.
terms of the reaction time and the TOF values. Therefore, Also, in order to clearly show the catalytic properties, the recy-
potassium hydroxide was selected as the optimal base (Table 4, cled catalyst in half time of the reaction was reused in the same
entry 2). In the nal step, the reaction temperature decreased
ꢀ
from 130 to 100 C, whose reaction yield reduced from 98% to
67% within 120 min (Table 4, entry 13). Based on the above-
mentioned studies, the optimal conditions for the synthesis of
ꢀ
ethers were obtained in DMSO as the solvent at 130 C in the
presence of 30 mg (2.12 mol%) of Cu–ninhydrin@GO–Ni MNPs
using potassium hydroxide as the base (Table 4, entry 2).
The obtained conditions for the coupling reaction of iodo-
benzene with phenol were extended to the coupling of other aryl
halides including aryl iodides, aryl bromides, and aryl chlorides
(Table 5). All the products were obtained with high TOF values
and good yields in short reaction times. Similar to the Suzuki
reaction in the presence of Cu–ninhydrin@GO–Ni MNPs, the
reactivity of aryl iodide in the C–O coupling reaction is higher
than that of aryl chloride or aryl bromide. As shown in Table 5, it
only takes 2 hours for the coupling of iodobenzene with phenol
to complete (Table 5, entry 1), while it takes 8 and 12 hours for
bromobenzenes and chlorobenzene to complete the reaction,
respectively (Table 5, entries 3 and 8). Therefore, the order of
reactivity of aryl halides in the synthesis of ethers in the pres-
ence of Cu–ninhydrin@GO–Ni MNPs is aryl iodides > aryl
bromides > aryl chlorides. Therefore, this catalyst can selectively with phenol in the presence of Cu–ninhydrin@GO–Ni MNPs.
Scheme 8 The catalytic cycle for the C–O coupling of aryl halides
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condition, which can be found in Tables 2 (entry 3) and 4 (entry
2). Aer the completion of each reaction, the catalyst was
recovered by the assistance of an external magnet. Then, to
study the reusability of this catalyst, the catalytic activity of the
recovered catalyst was evaluated in the next reaction again. The
obtained results are summarized in Fig. 8. As shown in Fig. 8,
this catalyst can be reused for atleast 8 runs consecutive in C–C
or C–O coupling reactions.
In order to show the efficiency of Cu–ninhydrin@GO–Ni
MNPs, the obtained results from the coupling of iodobenzene
or chlorobenzene with PhB(OH)2 in the presence of this catalyst
were compared with the previous methods (Table 6). As shown
in Table 5, the products were obtained in higher yield in
a shorter time than the other catalysts. Also, palladium catalysts
were employed as the catalyst in some of the methods, which is
very expensive and more toxic than the copper catalyst. In
addition, the Suzuki reaction was carried out in water as the
solvent in the presence of Cu–ninhydrin@GO–Ni MNPs;
meanwhile, toxic, expensive, and organic solvents were used in
other works. Also, the Suzuki reaction was reported in the
presence of homogeneous catalysts, which cannot be recovered
and reused. On the other hand, Cu–ninhydrin@GO–Ni MNPs
can be recovered by an external magnet and recycled for several
runs in C–C coupling reactions without a signicant loss of its
catalytic activity.
Fig. 8 Recyclability of Cu–ninhydrin@GO–Ni MNPs in the coupling of
((a) red line) 1-bromo-4-chlorobenzene with PhB(OH)2 and ((b) green
line) iodobenzene with phenol.
reaction, in which 90% of the product was obtained aer
270 min. Due to the heterogeneous nature of this catalyst, it can
be recovered and reused several times. The recoverability of the
catalyst is an importance factor for the evaluability of the
catalyst applications. Therefore, reusing Cu–ninhydrin@GO–Ni
MNPs was examined in the synthesis of both diaryl ethers and
biphenyls. In order to investigate this issue, the coupling of 1-
bromo-4-chlorobenzene with PhB(OH)2 and also the coupling of
iodobenzene with phenol in the presence of Cu–ninhy-
drin@GO–Ni MNPs were selected as the model reactions. At
rst, each of the reaction was started under the optimized
4 Conclusions
In summary, magnetic graphene oxide nanosheets using nickel
magnetic nanoparticles were synthesized via an inexpensive
Table 6 Comparison of Cu–ninhydrin@GO–Ni MNPs in the coupling reaction of chlorobenzene with PhB(OH)2 with the previously reported
procedures
Entry
Catalyst (mol%)
Aryl halide
Condition
Time (h)
Yield (%)
TOF (hꢂ1
)
Ref.
1
2
3
4
Pd(eao)2 (2 mol%)
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
NaHCO3, PEG400/H2O, 80 ꢀ
C
360
270
360
600
34
81
99
96
2.8
—
9.7
41
61
62
63
64
Pd NPs@Fe3O4–lignin
Pd@COF-QA (1.7 mol%)
Cross-linked poly(ITC-HPTPy)–Pd
(0.23 mol%)
K2CO3, EtOH : H2O, 90 ꢀ
C
TEA, H2O, 50 ꢀ
C
K2CO3, EtOH : H2O, 80 ꢀ
C
5
6
7
8
Pd(dba)2 (2.5 mol%)
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Click-triazole, NaOtBu,
toluene, 100 ꢀC
18
250
25
80
87
89
89
1.8
14
5
65
66
67
68
Pd–isatin–boehmite
(1.48 mol%)
Pd(0)TBA@biochar
(0.715 mol%)
Pd-imi-CC@MCM-41/Fe3O4
(1.5 mol%)
HMS–CPTMS–Cy–Pd
Cu–MPAMP@Fe3O4
Pd/Au NPs (4 mol%)
Pd NP (1 mol%)
Copper powder (10 mol%)
Cu–C (10 mol%)
Cu–C (20 mol%)
Cu–ninhydrin@GO–Ni MNPs
(2.12 mol%)
Cu–ninhydrin@GO–Ni MNPs
(2.12 mol%)
K2CO3, PEG, 80 ꢀ
C
Na2CO3, PEG, 80 ꢀ
Na2CO3, PEG, 80 ꢀ
C
C
24
2.5
9
Chlorobenzene
Iodobenzene
Iodobenzene
Iodobenzene
Iodobenzene
Iodobenzene
Chlorobenzene
Chlorobenzene
K2CO3, PEG, 100 ꢀ
Na2CO3, PEG, 80 ꢀ
C
C
300
100
24
12
12
3.3
240
240
84
97
88
95
99
96
15
90
12.9
51
0.9
7.9
0.8
2.9
0.2
10.61
69
70
71
72
73
74
74
This
work
This
work
10
11
12
13
14
15
16
EtOH/H2O, K2CO3, 80 ꢀC
H2O, KOH, 100 ꢀ
C
K2CO3, PEG, 110 ꢀ
C
H2O, K2CO3, 50 ꢀ
H2O, K2CO3, 50 ꢀ
N2CO3, H2O, 80 ꢀ
C
C
C
17
Iodobenzene
N2CO3, H2O, 80 ꢀ
C
50
97
54.90
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and fast procedure. Then, a copper catalyst was immobilized on 15 H. Veisi, A. Nikseresht, N. Ahmadi, K. Khosravi and
its surface (Cu–ninhydrin@GO–Ni MNPs) for the rst time. This F. Saeidifar, Polyhedron, 2019, 162, 240.
catalyst was characterized by SEM, WDX, EDS, TGA, FT-IR, XRD, 16 C. Christoph Tzschucke, C. Markert, W. Bannwarth,
AAS, and VSM techniques. The catalytic application of Cu–
ninhydrin@GO–Ni MNPs was conrmed in the C–C and C–O
S. Roller, A. Hebel and R. Haag, Angew. Chem., Int. Ed.,
2002, 41, 3964.
coupling reactions. The C–C coupling reaction was carried out 17 M. Kharazi, J. Saien, M. Yarie and M. A. Zolgol, J. Mol. Liq.,
in water in the presence of this catalyst, which is described as 2019, 296, 111748.
environment-friendly conditions. Also, aryl halides containing 18 M. Nikoorazm, N. Noori, B. Tahmasbi and S. Faryadi,
an electron-donating or electron-withdrawing group were Transition Met. Chem., 2017, 42, 469.
investigated in the C–C or C–O coupling reactions, which indi- 19 M. Hajjami and Z. Yousofvand, Catal. Lett., 2015, 145, 1733.
cate that this procedure is effective for a wide range of 20 R. Ghafouri-Nejad and M. Hajjami, React. Kinet., Mech.
substrates. The TOF values and yields of the products illustrated
the good efficiency of this catalyst. Also, this catalyst shows 21 R. Ghafouri-Nejad, M. Hajjami and R. Nejat, Appl.
a good selectivity in the synthesis of diaryl ethers and biphenyls. Organomet. Chem., 2018, 32, e4248.
The high stability and natural heterogeneity of Cu–ninhy- 22 A. Ghorbani-Choghamarani, P. Moradi and B. Tahmasbi, J.
Catal., 2020, 129, 371.
drin@GO–Ni MNPs were conrmed by the hot ltration test and
Iran. Chem. Soc., 2019, 16, 511.
the AAS technique.
23 S. Babaee, M. Zarei, H. Sepehrmansourie, M. A. Zolgol and
S. Rostamnia, ACS Omega, 2020, 12, 6240.
24 P. Moradi, M. Hajjami and B. Tahmasbi, Polyhedron, 2020,
175, 114169.
Conflicts of interest
The authors declare that they have no known competing 25 H. Sepahvand, E. Ghasemi, M. Sharbati, M. S. Mohammadi,
nancial interests or personal relationships that could have
appeared to inuence the work reported in this paper.
M. Arshadi Pirlar and G. H. Shahverdizadeh, New J. Chem.,
2019, 43, 16555.
26 P. Zhou, D. Li, S. Jin, Sh. Chen and Z. Zhang, Int. J. Hydrogen
Energy, 2016, 41, 15218.
27 C. Su, Sh. Zhao, P. Wang, W. Chang, K. Chang and H. Zhang,
J. Environ. Chem. Eng., 2016, 4, 3433.
Acknowledgements
Authors thank Ilam University, Bu-Ali Sina University and Iran
National Science Foundation (INSF) for nancial support of this 28 F. Faghiri, M. Hajjami and F. Ghorbani, Sens. Actuators, B,
research project.
2021, 343, 130157.
29 A. Maleki, R. Taheri-Ledari, R. Ghalavand and R. Firouzi-
Haji, J. Phys. Chem. Solids, 2020, 136, 109200.
30 M. Munoz, Z. M. de Pedro, J. A. Casas and J. J. Rodriguez,
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© 2021 The Author(s). Published by the Royal Society of Chemistry
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