Preparation and Characterization of Ni-Modified Graphene Oxide Complex as an Efficient Catalyst for the Synthesis of Sulfides via Reaction of Arylhalides with S8 or Thiourea

Article abstract of DOI:10.1002/aoc.4248

In this work, complex of Ni-modified graphene oxide was prepared and characterized using FT-IR spectroscopy, SEM, XRD, TGA and ICP-OES techniques. This compound used as an efficient and recoverable catalyst for the C–S coupling reaction using sulfur-transfer reagents (S₈ or thiourea). The catalyst was easily separated using a simple filtration and reusable without significant loss of their catalytic efficiency.

Full text of DOI:10.1002/aoc.4248

Received: 12 September 2017
DOI: 10.1002/aoc.4248
Revised: 2 December 2017
Accepted: 4 December 2017
F U L L P A P E R
Preparation and Characterization of Ni‐Modified Graphene
Oxide Complex as an Efficient Catalyst for the Synthesis of
Sulfides via Reaction of Arylhalides with S8 or Thiourea
Raziyeh Ghafouri‐Nejad1 | Maryam Hajjami1
| Razieh Nejat2
1 Department of Chemistry, Faculty of
In this work, complex of Ni‐modified graphene oxide was prepared and charac-
terized using FT‐IR spectroscopy, SEM, XRD, TGA and ICP‐OES techniques.
This compound used as an efficient and recoverable catalyst for the C–S cou-
pling reaction using sulfur‐transfer reagents (S8 or thiourea). The catalyst was
easily separated using a simple filtration and reusable without significant loss
of their catalytic efficiency.
Science, Ilam University, PO Box
69315516, Ilam, Iran
2 Department of Chemistry, Faculty of
Science, Kosar University of Bojnord, PO
Box 9415615458, Bojnord, Iran
Correspondence
Maryam Hajjami, Department of
Chemistry, Faculty of Science, Ilam
University, PO Box 69315516, Ilam, Iran.
Email: mhajjami@yahoo.com;
m.hejami@ilam.ac.ir
KEYWORDS
aryl halide, graphene oxide, sulfides, thiourea
Funding information
Ilam University
1 | INTRODUCTION
network.[11,12] GO used in various fields of biological,[13]
optical,[14] electrical,[15] thermal and mechanical.[16] The
Recently, the design of efficient, recoverable and recyclable
catalysts has become an important in organic reactions.[1]
General method to arrive this goal is the immobilization
of homogeneous catalysts on nanomaterials as heteroge-
neous supports.[2] When the size of the support is
decreased to the nanometer scale, the surface area is
increased.[3,4] Therefore, nanocatalysts can be used as
bridge to improve the gap between homogeneous and het-
erogeneous catalysis for combine the advantages of both
catalysis.[5] Some nanomaterial such as mesoporous silica
material, nanoboehmite and ionic liquids were applied as
support. But preparations of many supports required a lot
of time and are more expensive, also mesoporous silica
required high temperature for calcination.[6,7] Carbon
nanomaterials have been considered for use as support
materials due to its tensile strength, large surface area,
thermal stability, ease of recovery and recyclability.[8]
Graphene is one of carbon allotropes which used as sup-
port for preparation of heterogeneous catalysts.[8,9] One
of the most important derivatives of graphene is graphene
oxide (GO),[10] that including a 2‐dimensional single‐layer
sheet with a hexagonal structure ring based carbon
key advantages of GO are high specific surface area,[17]
high surface‐to‐volume ratio[18] and chemical stability.[19]
Graphene oxide, prepared by complete oxidation of graph-
ite, contains various functional groups such as epoxy,
hydroxyl, carbonyl, and carboxyl groups.[20]
Diaryl sulfides and their derivatives are important in
intermediates organic synthesis, medicinal chemistry
and biologically active molecules.[21] Also have widely
applications in the treatment of diseases such as HIV,[22]
cancer,[23] Parkinson's, diabetes and Alzheimer.[24]
Diaryl sulfides can be synthesized by cross‐coupling
reaction of aryl halides with sulfides catalyzed by
transition‐metals such as MCM‐41‐immobilized bidentate
nitrogen copper (I) complex (MCM‐41‐2 N‐CuI),[23]
PdNP‐PNF,[25] MCM‐41‐immobilized 1,10‐phenanthroline‐
copper (II) complex,[26] Fe3O4@SiO2@His@Ni(II).[27]
Traditional methods for the synthesis of these
compounds include the reaction between thiols with
aryl/alkyl halides. The main limitations of these methods
including direct use of highly volatile, toxic and
foul smelling thiols, which leads to unavoidable environ-
mental and safety problems, that can act as metal
Appl Organometal Chem. 2018;e4248.
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Copyright © 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4248

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GHAFOURI‐NEJAD ET AL.
deactivators due to their tendency to bind to transition
metals. In addition, thiols get easily oxidized to their sta-
ble disulfides which are the major byproducts in most of
the C‐S cross‐coupling reactions.[28–31] In order to over-
come this disadvantage, various sulfur reagents such as
thiourea,[25] potassium thiocyanate,[32] carbon disul-
fide,[33] sulfur powder[34] and sodium thiosulfate[35] have
been applied in the synthesis of sulfides. Among sulfur
reagents, S8 shows particular promise for S‐arylation,
due to its low cost and being odorless.[36,37] and also thio-
urea is a cheap, safe and effective sulfur transfer agent.[38]
In this paper we report the first synthesis of complex
of Ni‐modified graphene oxide and studied its successful
application to C‐S coupling reaction between aryl halides
and S8 or thiourea.
and used without further purification. IR spectra were
recorded as KBr pellets on a VRTEX 70 model
BRUKER FT‐IR spectrophotometer. The thermogravi-
metric analysis (TGA) was used with a heating rate
of 10 °C/min in air and the samples were heated from
room temperature to 750 °C. X‐ray diffraction (XRD)
patterns were recorded using a Cu Ka radiation source
with wave length 1.54 Å. The particle size and mor-
phology were examined by measuring SEM using
FESEM‐TESCAN. The content of Ni was measured by
inductively coupled plasma‐optical emission spectrome-
try (ICP‐OES).
2.2 | Synthesis of graphene oxide
Graphene oxide was synthesized using graphite pow-
ders by modified Hummer's method.[39] In a typical
synthesis process, 1 g of graphite powder and 0.5 g of
sodium nitrate mixed together and then 23 ml of con-
centrated sulfuric acid was added slowly in an ice bath
and mixture was stirred 15 min. Then 3 g of potassium
permanganate was gradually added under stirring to
2 | EXPERIMENTAL
2.1 | Materials and Instrumentation
All reagents and solvent used in this work were buying
from Sigma‐Aldrich and Merck chemical companies
SCHEME 1 Ni (II)‐modified‐GO synthesis

GHAFOURI‐NEJAD ET AL.
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the suspension at 0 °C for 1.5 h and then at 35 °C was
stirred for 2 h. During stirring, 46 ml of deionized
water was slowly added to the solution and the solu-
tion temperature was kept at 98 °C and stirred for
30 min. Finally, the reaction was stopped by addition
of 140 ml of deionized water and 10 ml of 30% hydro-
gen peroxide. The resulting solution was washed with
HCl 10% and deionized water then centrifuged several
times. The graphite oxide was obtained by filtration
and dried under vacuum at 50 °C for 24 h. Finally,
the graphite oxide was dispersed in deionized water
and exfoliated by ultrasound for 30 min to generate
GO (0.7 g) nanosheets.
3 | RESULTS AND DISCUSSION
3.1 | Catalyst Synthesis and
Characterization
After preparation of the Ni (II)‐modified‐GO, the catalyst
was characterized by some microscopic and spectroscopic
techniques including FT‐IR spectroscopy, XRD, TGA,
SEM, EDX and ICP‐OES.
The FT‐IR spectra of GO, GO‐NH2, GO‐N‐isatin,
GO‐N‐ isatin‐Ni (II) samples are shown in Figure 1. The
FT‐IR spectrum of GO was shown in Figure 1a. The peak
at about 1586 cm‐1 is attributed to C=C double bonds.
Also, this spectrum shows the peaks at 1047, 1726 and
3425 cm−1 which could be appointed to carbon–oxygen,
carbonyl, and hydroxyl stretching mode of functional
groups such as epoxy, carboxylic acid, and hydroxyl
groups attachment to GO nano sheets, respectively.[17]
The GO‐NH2 spectrum was shown in Figure 1b. The
Si–O–Si bond, asymmetric stretching vibration and sym-
metric stretching vibration, appear at 1030 cm‐1 and
723 cm‐1, respectively. Also, N–H bending vibration
appears at 1516 cm‐1 and 1617 cm‐1, which the presence
of the N‐propylamine was confirmed. In the FT‐IR spectra
of GO‐N‐isatin (Figure 1c), the existence of the grafted
isatin group is identified by C=N vibrations that appear
at 1620 cm−1, which this band has been shifted to lower
frequency (1614 cm−1) in the catalyst (Figure 1d), which
2.3 | Synthesis of complex of Ni (II)‐
modified‐GO
The obtained GO powder (1 g) was dispersed in toluene
for 2 h. Then 1 mL 3‐aminopropyltriethoxysilane (99%)
was added to the mixture under N2 atmosphere and
refluxed for 24 h. Then resulting product was filtered,
washed with dichloromethane and dried in a vacuum
at 60 °C for 10 h to obtain aminofunctionalized GO
(1.1 g) (GO‐nPr‐NH2). Then 2 mmol (0.294 g) isatin
and a few drops of acetic acid were added to 1 g of
GO‐nPr‐NH2, under N2 atmosphere. The mixture was
refluxed for 48 h. The resultant was washed with etha-
nol several times and dried in an oven to obtain GO‐
N‐isatin (1.25 g). Finally, Ni(NO3)2.6H2O (2 mmol) was
added to GO‐N‐isatin (1 g), under N2 atmosphere and
refluxed for 48 h. Then the resulting product was
washed with ethanol and deionized water several times
and dried in an oven to obtain GO‐N‐isatin‐Ni(II)
(1.2 g) (Scheme 1).
2.4 | General procedure for preparation of
sulfides
A mixture of Catalyst (0.03 g), thiourea/S8 (0.5 mmol),
aryl halide (1 mmol) and NaOEt (0.8 g) was stirred at
120 °C in DMSO (2 mL). The progress was monitored
by TLC. On completion, the reaction mixture was
cooled at room temperature. Ethyl acetate and water
were added to the mixture. The excess of sulfur dis-
solved in water and removed from reaction mixture.
The catalyst was separated by simple filtration. Then
the residue was extracted with ethyl acetate and dried
with anhydrous Na2SO4, the organic layer was evapo-
rated under reduced pressure to attain the correspond-
ing sulfide. For more purification the preparative TLC
was used.
FIGURE 1 FT‐IR spectra of a) GO b) GO‐NH2 c) GO‐N‐isatin d)
GO‐N‐isatin‐Ni (II)

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GHAFOURI‐NEJAD ET AL.
indicates the formation of nickel complex on surface of
functionalized GO nano sheets.
GO nanosheets.[19] In TGA curve of the GO‐N‐isatin‐Ni
(II), a weight loss (8%) before 200 °C is due to the
trapped water and also a weight loss about 20% from
250 to 700 °C attributed to the decomposition of
immobilized organic spaces on the GO nanosheets
surface.
SEM image of the GO‐N‐isatin‐Ni at different magnifi-
cations are shown in the Figure 4 that display the well‐
defined morphology of nanosheets. The GO‐N‐isatin‐Ni
is clearly observed as exfoliate structures with wrinkled
forms.
The energy dispersive X‐ray spectrum (EDX) of GO‐N‐
isatin‐Ni shows in Figure 5 that was confirmed the per-
cent of C, N, O, Si and Ni elements in the catalyst.
Also based on inductively coupled plasma atomic
emission spectroscopy (ICP‐OES), the amounts of Ni
(II) in the Ni (II)‐modified‐GO (catalyst) is
0.158 mmol.g‐1. Also to investigate leaching of the Ni
species, the reaction of iodobenzene with S8 in the
synthesis of diaryl sulfides was examined. In typical
test, the catalyst was filtered and the recovered catalyst
after 5 runs. Then the recovered catalyst after 5 runs
was analyzed nickel content using ICP‐OES. The
amounts of Ni (II) obtained 0.127 mmol.g‐1. Therefore,
after five runs 0.031 mmol.g‐1 leaching of catalyst was
observed, which indicated Ni leaching of the catalyst
was very low.
Figure 2 shows XRD patterns of GO and GO‐N‐isatin‐
Ni (II). The XRD pattern of GO shows a strong peak at
approximately 2θ = 11.15° which corresponds to inter-
layers spacing of 0.79 nm. This large interlayer distance
is due to the presence of carboxyl, epoxy and hydroxyl
groups.[9] Also, the XRD pattern GO‐N‐isatin‐Ni (II) has
very similar peaks to GO suggesting their similar crystal
structure of the graphene oxide layers.
Figure 3 shows the TGA analysis of GO and GO‐N‐
isatin‐Ni. The results were confirmed by TGA analysis
data by showing 6% weight loss before 130 °C for GO,
which is caused by the release of trapped water between
layers GO nanosheets. Also the weight loss (23%)
between 130 °C and 212 °C is due to the decomposition
of the labile oxygen‐containing functional groups
(hydroxyl, carboxylic acid and epoxy) on the surface of
3.2 | Catalytic studies
The prepared catalyst was assessed for its activity in the
C‐S coupling reaction. In order to optimize the reaction
conditions, the reaction of iodobenzene with S8 in the
presence of Ni (II)‐modified‐GO has been selected as a
model reaction and different parameters including the
type of base, solvent and temperature have been studied
(Table 1). In order to choose the reaction media, differ-
ent solvents such as PEG, DMF, DMSO, and CH3CN
were used (Table 1, entries 3–6) and the best results
were obtained in DMSO using 0.03 g of Ni (II)‐modi-
fied‐GO (Table 1, entry 3). The reaction was significantly
affected by the nature of base. Therefore, to found the
best reaction condition, the effect and amount of base
were described (Table 1, entries 7–12) and the best result
was obtained using 0.8 gr of NaOEt. When the amount
of NaOEt was reduced to 0.5 and 0.3 g, the yield of
the reaction decreased to 65 % and 35%, respectively.
Also, the effect of temperature was described (Table 1,
entries 13–14) and the best results were obtained at
120 °C. Therefore, as listed in Table 1, iodobenzen
(1 mmol) in the presence of catalytic amount of Ni
(II)‐modified‐GO (0.03 g) using S8 (0.5 mmol) and
NaOEt (0.8 gr) in DMSO at 120 °C was found to be ideal
FIGURE 2 XRD pattern of GO and GO‐N‐isatin‐Ni (II)
FIGURE 3 TGA analysis of GO and GO‐N‐isatin‐Ni (II)

GHAFOURI‐NEJAD ET AL.
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FIGURE 4 SEM images of GO‐N‐isatin‐Ni(II) at different magnification
TABLE 1 Optimization of the reaction conditionsa
Yieldb (%)
Catalyst
Entry (g)
Temp.
(°C)
Solvent Base (gr)
S8 / thiourea
1
0.01
0.02
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
DMSO NaOEt (0.8) 120
DMSO NaOEt (0.8) 120
DMSO NaOEt (0.8) 120
67 / 60
2
80 / 75
3
97c / 95
4
DMF
PEG
NaOEt (0.8) 120
NaOEt (0.8) 120
N.R / N.R
N.R / N.R
N.R / N.R
45 / 70
5
6
CH3CN NaOEt (0.8) 120
DMSO KOH (0.8) 120
7
FIGURE 5 The EDX spectrum of GO‐N‐isatin‐Ni (II)
8
DMSO K2CO3 (0.8) 120
DMSO Na2CO3 (0.8) 120
N.R / N.R
N.R / N.R
N.R / N.R
65 / 60
9
in the reaction conditions for the formation of corre-
sponding sulfide.
10
11
12
13
14
DMSO Et3N (0.8)
120
DMSO NaOEt (0.5) 120
DMSO NaOEt (0.3) 120
DMSO NaOEt (0.8) 130
DMSO NaOEt (0.8) 100
After optimization of the reaction condition, the vari-
ous aryl halides including several of functional groups
with S8 or thiourea have been described in optimum con-
dition and diaryl sulfides were obtained in short reaction
times with good to excellent yields (Table 2).
In a study, we examined the reaction of iodobenzene
with S8 using GO and Ni(II) separately at the same reac-
tion condition of Ni (II)‐modified‐GO. The results are
35 / 40
97 c / 96 c
75 / 70
aReaction conditions: iodobenzene (1 mmol), S8 or thiourea (0.5 mmol), time
for S8 30 min and for thiourea 4 h.
bpurification by preparative TLC.
cIsolated yield.

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GHAFOURI‐NEJAD ET AL.
TABLE 2 The reaction of various aryl halides with S8/thiourea for the synthesis of symmetrical diaryl sulfidesa
Time (h)
Yield (%)b
Entry
Aryl halide
Product
S8 / thiourea
S8 / thiourea
M.p (ref)
[27]
1
0.5 / 4
97 / 95
Colorless liquid
2
3
4
5
6
3/‐
N.R.c/‐
25(65)d/‐
90 / 91
93 / 94
96 / 73
‐
[27]
0.5(3)/‐
4 /6
Colorless liquid
[27]
Colorless liquid
[27]
2 / 5
Colorless liquid
0.75 / 3
Yellow liquid
[27]
7
1.5 / 4
90 / 75
Yellow liquid
[25]
8
9
3 / 3
4 / 5
90 / 85
93 / 90
Yellow liquid
[21]
Yellow liquid
[27]
10
11
12
1 / 1.5
2 / 1
85 / 86
87 / 80
85 / 75
160‐162
[27]
160‐162
[25]
5 / 7
156‐158
[33]
13
1.5 / 3.5
85 /83
Yellow liquid
(Continues)

GHAFOURI‐NEJAD ET AL.
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TABLE 2 (Continued)
Time (h)
S8 / thiourea
2 / 3.5
Yield (%)b
S8 / thiourea
88 / 90
Entry
Aryl halide
Product
M.p (ref)
[40]
14
43‐46
15
16
2 / 5
90 / 85
Oil [40]
2 /‐
87e /‐
Oil [41]
aReaction conditions: aryl halides (1 mmol), S8/thiourea (0.5 mmol), NaOEt (0.8 g), catalyst (30 mg) and DMSO (2 ml).
bIsolated yields.
cIn the presence of GO as catalyst.
dIn the presence of Ni (II) as catalyst.
ecatalyst (50 mg).
presented in Table 2 entries 2 and 3. As shown in Table 2
entry 2, in the presence of GO, after 3 h, the reaction was
not occurred and nothing happened. Also in the presence
of Ni (II) without support after 0.5 h the reaction did not
completed and the yield of 25% obtained by purification
with preparative TLC. Even after a longer time, 3 h, reac-
tion did not completed (65 %) and the product purifica-
tion performed by preparative TLC (Table 2, entry 3).
Experimental results show that halide derivatives with
different functional groups, such as methoxy, methyl,
chloro, nitro and etc. provide good to excellent yields.
As can be seen, aryl chlorides were not as reactive as aryl
bromides and iodides. Our results reveal that substitution
played a major role in governing the reactivity of the
substrate. Generally, synthesis of sulfide with electron‐
withdrawing groups has shorter reaction time than
electron‐donating ones. Also, the reaction times were
sensitive to steric effects of the aryl halides. A sterically
hindered ortho‐substituted aryl halide proved to be prob-
lematic for this catalyst system and gave a much longer
time than the other substrates. In the case of heterocyclic
and aliphatic halides the reaction is accomplished in
good times and yields (Table 2, entries 13, 14).
than the chloride group (Table 2, entry 15). The mass spec-
trum of the product is confirmed this fact (Figure 6).
In another study, to show the homoselectivity of the
described system, 1,4‐dibromo benzene was subjected to
the synthesis of sulfide. It is of interest that only one of
the bromides reacts selectively in the course of the reac-
tion and 4,4′‐dibromo diphenyl sulfide is produced
homoselectively (Table 2, entry 16). The mass spectrum
of the product is confirmed this fact (Figure 7).
3.3 | Reusability and recycling of the
catalyst
Reusability and recyclability of the catalyst was examined
through reaction of iodobenzene with S8 as a model reac-
tion. After completion of the reaction, the catalyst was
recovered by simple filtration from the reaction mixture
and washed with ethyl acetate to remove the residual
product. The recovered catalyst was dried and reused for
the next run. As shown in Figure 8, the catalyst can be
reused up to 5 runs without any significant loss of activity.
In order to investigate the chemoselectivity of
described method, the reaction of 1‐bromo‐4‐chloro ben-
zene as dihalogenated aryl halide with S8 or thiourea was
also examined which the bromide showed more reactivity
3.4 | Comparison of the catalyst
In order evaluate the catalytic activity of Ni (II)‐
modified‐GO, we compared the results for the synthesis

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GHAFOURI‐NEJAD ET AL.
FIGURE 6 The mass spectrum of 4,4′‐Dichloro diphenyl sulfide
FIGURE 7 The mass spectrum of 4,4′‐Dibromo diphenyl sulfide
of diaryl sulfide in the presence of described catalyst
with previously reported methods in the literature
(Table 3). This results show that Ni(II)‐modified‐GO
afford short reaction time and higher yield than other
catalysts. Even in the case of the same metal (Ni) but
in different back bone, in comparison of Fe3O4 with
spherical shapes and GO with 2‐dimensional single‐layer
sheet with a hexagonal structure ring based carbon net-
work, the GO based catalyst shows better results in both
yield and time.

GHAFOURI‐NEJAD ET AL.
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ORCID
Maryam Hajjami http://orcid.org/0000-0002-5225-4809
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