Design, synthesis, and catalytic performance of modified graphene oxide based on a cobalt complex as a heterogenous catalyst for the preparation of aminonaphthoquinone derivatives

Article abstract of DOI:10.1039/d1ra01790j

We are reporting a functionalized graphene oxide catalyst developed by modifying graphene oxide surface using the covalent attachment of an amino-functionalized SiO₂sphere/cobalt complex. Silica network has special characteristics including mechanical strength, high thermal and chemical stability with good dispersion in solvents. The silica/graphene oxide mixture provides improved properties and extends the scope of application. Graphene oxide was functionalized by spherical silica with the help of hybrid silane-containing nitrogen to coordinate with Co(ii) for increasing the catalytic activity. The catalyst was characterized by Fourier Transform Infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), Energy Dispersive X-ray (EDX), Scanning Electron Microscopy (SEM), Raman spectroscopy, and Thermal Gravimetric (TGA) analyses. The catalyst showed high catalytic activity for multi-component reactions in the synthesis of aminonaphthoquinones in ethanol solvent. The catalyst's ability to improve the yield (96-98%), reduce the reaction time (5-8 min), and recycling ability are important benefits for the catalyst.

Full text of DOI:10.1039/d1ra01790j

RSC Advances
View Article Online
View Journal | View Issue
PAPER
Design, synthesis, and catalytic performance of
modified graphene oxide based on a cobalt
complex as a heterogenous catalyst for the
preparation of aminonaphthoquinone derivatives†
Cite this: RSC Adv., 2021, 11, 17108
Mahnaz Mirheidari
and Javad Safaei-Ghomi
*
We are reporting a functionalized graphene oxide catalyst developed by modifying graphene oxide surface
using the covalent attachment of an amino-functionalized SiO sphere/cobalt complex. Silica network has
2
special characteristics including mechanical strength, high thermal and chemical stability with good
dispersion in solvents. The silica/graphene oxide mixture provides improved properties and extends the
scope of application. Graphene oxide was functionalized by spherical silica with the help of hybrid
silane-containing nitrogen to coordinate with Co(II) for increasing the catalytic activity. The catalyst was
characterized by Fourier Transform Infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), Energy
Dispersive X-ray (EDX), Scanning Electron Microscopy (SEM), Raman spectroscopy, and Thermal
Gravimetric (TGA) analyses. The catalyst showed high catalytic activity for multi-component reactions in
the synthesis of aminonaphthoquinones in ethanol solvent. The catalyst's ability to improve the yield
(96–98%), reduce the reaction time (5–8 min), and recycling ability are important benefits for the catalyst.
Received 6th March 2021
Accepted 3rd April 2021
DOI: 10.1039/d1ra01790j
rsc.li/rsc-advances
sheets. Therefore, graphene oxide is widely used as a catalyst
1
. Introduction
12,13
support.
Graphene is one form of carbon material with 2D layered cations in biomedical, electrochemical, and chemical elds.
structure that is considered as an excellent catalyst support in In addition, functionalized GO with various metals has been
Functionalized graphene oxide has several appli-
14
15,16
recent decades. Geim and Novoselov explored a single layer of extensively used for organic transformations.
1
graphene through crystal graphite in 2004 for the rst time.
As far as we know, among different surface modifying
Graphene has different applications in various elds including agents, polysiloxane-like silane coupling agents are oen
2
3
17,18
solar cells, polymer nanocomposites, and biological nano- applied to obtain modied graphene sheets.
During the
4
composites due to its elasticity, chemical stability, and high coupling procedure, the covalent bonds between the functional
specic surface area as well as electrical and heat groups of silane with graphene oxide lead to increased gra-
5
–7
conductivity.
Graphene oxide (GO) is the oxidised form of graphene, which multifunctional characteristics.
phene oxide performance in the catalytic eld and deliver
19–21
2
Silica (SiO ) increases the
has a two-dimensional monolayer honeycomb structure. It is corrosion resistance and thermal resistance of graphene oxide,
a good precursor material for fabrication in large quantities due which may improve the loading of catalytically active sites,
22–27
to its low-cost and easily scalable synthesis process. In addition, having signicant application potential in different elds.
modication of graphene oxide is simple due to chemical In addition, cobalt has obtained more attention because of
2
8,29
interaction between oxygen functional groups on the surface, being an earth-abundant metal, catalytic activities,
and
8
–10
30
making it a desirable support in chemical reactions.
methods have been developed for GO synthesis, however,
2
Several photocatalytic H production.
2-Hydroxy-1,4-napthoquinone (lawsone) has been known for
almost 4000 years, which is present in the leaves of the henna
The oxygen-containing functional groups that are distrib- plant, and it is a signicant source of natural dyes. The
uted over the GO surface can act as an active site, and can be compounds containing the naphthoquinone structure received
attacked by nucleophiles to change the surface of graphene a great deal of attention because of various biological features
11
Hummers' method is the most well-known approach.
31
32
33
such as molluscicidal, antitumor, antifungal, and antibac-
34
35
terial activities as well as uorescence behavior.
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, P.O.
Box 87317-51167, Kashan, I. R. Iran. E-mail: safaei@kashanu.ac.ir
Research shows that the incorporation of nitrogen atom
containing functional groups such as amino group or nitrogen
†
Electronic supplementary information (ESI) available. See DOI:
0.1039/d1ra01790j
1
17108 | RSC Adv., 2021, 11, 17108–17115
© 2021 The Author(s). Published by the Royal Society of Chemistry

View Article Online
Paper
RSC Advances
measurements were carried out on a Magna 550 instrument by
1
13
using potassium bromide (KBr) plates. The H NMR and
C
NMR spectra were determined on a Bruker Avance-400 spec-
trometer with DMSO-d . The X-ray diffraction patterns were
6
collected on an X-ray diffractometer (PHILIPS, PW 1510, Neth-
erland). Scanning Electron Microscopy and Energy Dispersive X-
ray analysis (MIRA3-TESCAN FESEM) was used to provide
information about morphology and elemental composition.
Raman spectra were recorded using a Takram N1-541 Raman
spectrometer (Teksan, Tehran, Iran). Thermal analysis was
carried out on a STA 503 (Bahr) instrument.
2.2. Synthesis of graphene oxide
Graphite powder (1 g) along with 0.5 g sodium nitrate were
dissolved in 25 ml of sulphuric acid (98%) for 10 minutes and
then 3 g potassium carbonate was added to the mixture while
ꢀ
the temperature increased to 35 C with further stirring for
3
0 min. Aerward, the solution was added to DI water (100 ml)
ꢀ
and stirred for 15 minutes at 95 C. Then, 10 ml (30% w/w) H O
2
2
was added to the solution. The obtained brown solution was
centrifuged, washed thoroughly with HCl and DI water, and
ꢀ
dried at 60 C for 12 h. Finally, the dried solid was dispersed in
distilled H
2
O by sonication, then centrifuged and dried again at
ꢀ
60 C for 24 h.
2.3. Synthesis of spherical silicon dioxide nanoparticles
The mixture of EtOH (50 ml) and DI water (20 ml) was ultra-
sonicated for 30 minutes. Then, the solution of tetraethyl
orthosilicate (3 ml) and PVP (0.1 mmol) in 5 ml ethanol was
added dropwise to a mixture by vigorous stirring. Ethylenedi-
amine (0.1 ml) as a precipitating agent was slowly added to the
solution under sonication. Aer 30 minutes, the obtained
silicon dioxide (SiO
2
) was collected and washed thoroughly with
ꢀ
EtOH and H O and then was dried at 80 C.
2
2
Scheme 1 Different steps of synthesis of f-SiO @GO@Co.
2.4. Synthesis of ethylenediamine group@silicon dioxide
atom into the naphthoquinone framework oen improves
anticancer, molluscicidal, and antibacterial activities.
Considering the above-mentioned properties of graphene
oxide, in the current study, the GO surface was activated with
At rst, reuxing silicon dioxide (1 g) with 0.5 ml 3-chloropropyl
triethoxysilane (CPTES) was done in 30 ml dry toluene for 24 h.
The obtained product was centrifuged and washed with toluene
36
37
38
ꢀ
several times and then dried for 8 h at 120 C. Then, 0.3 g
2
amino-functionalized SiO containing binding sites for coordi-
ethylenediamine was added to a solution containing 1 g of
nation to Co(II) for increasing the catalytic activity. The
produced catalyst as the highly efficient heterogeneous catalyst
was used for the synthesis of aminonaphthoquinone derivatives
through a three-component condensation reaction of lawsone,
aromatic aldehydes, and aromatic amines in the presence of
ethanol at room temperature (Scheme 1).
SiO @CPTES in 30 ml EtOH and reuxed for 24 h. The obtained
2
solid was ltered and washed with water and EtOH and nally
ꢀ
dried for 10 h under 90 C.
2.5. Synthesis of ethylenediamine-functionalized
SiO @graphene oxide
2
0
2
.04 g GO, 20 ml DI water, and 0.16 g SiO @ethylenediamine
2
. Experimental
were added to a round-bottom ask and dispersed under
ultrasonic irradiation for 20 minutes. Then, the sonicated
2.1. General
ꢀ
All materials were commercially purchased from Merck and solution was stirred for 12 h at 85 C and the solid material was
Sigma-Aldrich. Melting points of the products were recorded by centrifuged, washed with EtOH and DI water to remove impu-
an Electrothermal 9200 system. Fourier transform infrared rities, and dried overnight at 60 C.
ꢀ
©
2021 The Author(s). Published by the Royal Society of Chemistry
RSC Adv., 2021, 11, 17108–17115 | 17109

View Article Online
RSC Advances
Paper
2
.6. Synthesis of ethylenediamine-functionalized
SiO @graphene oxide@cobalt
g ethylenediamine-functionalized SiO
.01 wt% cobalt(II) chloride and 5 ml absolute EtOH were added
2
1
0
2
@graphene oxide,
to a ask and dispersed under ultrasound for 5 minutes to
obtain a uniform dispersion aer mixing. The uniform mixture
was stirred at RT for 24 h. The nal product was then separated
and washed with EtOH and DI water and dried at RT.
2.7. General procedure for the synthesis of
aminonaphthoquinone derivatives
To a mixture of lawsone (1 mmol) and the respective amine (1
mmol) in ethanol (5 ml), 20 wt% catalyst was added. Aer
stirring for 10 minutes at room temperature (RT), the corre-
sponding benzaldehyde (1 mmol) was added and stirred until
the reaction was completed (monitored by TLC). The produced
solid was puried by cold ethanol and water to afford the pure
product.
Fig. 2 XRD patterns of GO, f-SiO
2
@GO, and f-SiO
2
@GO@Co.
3
. Results and discussion
vibrations, carbonyl stretch for carboxylic acid, C–O stretching,
and epoxy group vibrations, respectively. For SiO , the absorp-
tion peaks at 798, 1089 cm , and 3370 cm were attributed to
3.1. Characterization of catalyst
2
ꢁ1
ꢁ1
The synthesized catalyst (f-SiO @GO@Co) includes the prop-
erties of functionalized SiO
distinct steps for the catalyst is presented in Fig. 1. Graphene
oxide showed peaks at 3398 cm , 1721 cm , 1383, and
2
asymmetric vibrations of the Si–O–Si bonds and O–H groups. In
2
and GO. The FT-IR spectrum of
SiO
2
@Cl and SiO
2
@ethylenediamine spectra, the bands at
ꢁ1
around 950 cm were related to ethoxy stretching vibrations.
ꢁ1
ꢁ1
Aer graing functionalized SiO
band at 1102 cm conrmed the successful formation of f-
2
onto graphene oxide, the
ꢁ
1
1060 cm , which were attributed to the O–H group stretching
ꢁ1
SiO @GO@Co.
2
The XRD pattern for graphene oxide sheets showed a strong
ꢀ
peak at about 2q ¼ 12 , which revealed the exfoliation of GO and
intercalation of water molecules in the graphite structure such
39
that oxygen functional groups result between graphite layers.
Aer the functionalization of graphene oxide, the removal of
many oxygen-containing functional groups on the surface of
ꢀ
graphene oxide cause the intensity of the peak at 2q ¼ 12 to
ꢀ
ꢀ
decrease. Also, the broad peak at 2q ¼ 25 and 2q ¼ 44 corre-
sponded to the amorphous silica and Co, which suggests the
successful synthesis of the desired catalyst (Fig. 2).
The SEM analysis for graphene oxide (Fig. 3a) shows the
layered structure with crumpled morphology at the sheet edges.
2 2 2 2 2
Fig. 1 FT-IR spectra of SiO , SiO @Cl, SiO @NH , GO, f-SiO @GO,
and f-SiO @GO@Co.
2
2
Fig. 3 FE-SEM images of GO (a) f-SiO @GO@Co (b).
17110 | RSC Adv., 2021, 11, 17108–17115
© 2021 The Author(s). Published by the Royal Society of Chemistry

View Article Online
Paper
RSC Advances
2
Fig. 4 EDS spectra of GO (a) and f-SiO @GO@Co (b).
D
Functionalized graphene oxide (Fig. 3b) exhibits the distribu- for functionalized graphene oxide showed similar peaks, while I /
tion of functionalized spherical silica nanoparticles on the
surface of graphene oxide sheets.
I
G
ratio increased compared to I
D
/I
G
of graphene oxide, indicating
@GO@Co from the
3
the formation of more sp carbon in f-SiO
2
41,42
The EDX analysis for graphene oxide and f-SiO
2
@GO@Co graing of f-SiO
2
on graphene oxide.
catalyst are presented in Fig. 4. According to the data for gra-
Thermogravimetric analysis (TGA) of the catalyst was carried
phene oxide EDX (Fig. 4a), the carbon and oxygen contents for out and the result is shown in Fig. 6. The TGA spectrum of
graphene oxide (atomic percentage) were 64.78% and 35.22%, graphene oxide shows that it is unstable, with weight loss even
ꢀ
43
respectively, and the ratio of carbon to oxygen was C/O ¼ 1.83. The below 100 C corresponding to the removal of absorbed water.
atomic percentage of C, N, O, Si, Cl, Co was 32.62%, 3.82%, 48.92%, In TGA of the catalyst, the primary loss occurred at around
4.30%, 0.17%, 0.16%, respectively. In the elemental analysis of f- 200 C, which was attributed to the pyrolysis of the functional
@GO@Co, SiO moiety in the catalyst structure reduced the groups containing oxygen. Decomposition of the catalyst aer
2 2
carbon amount (32.62%) and increased the oxygen amount 230 C, that continues to 800 C indicated the thermal stability
ꢀ
1
44
SiO
ꢀ
ꢀ
40
(
48.92%), which resulted in a carbon to oxygen ratio of C/O ¼ 0.66.
The Raman spectra were used for the identication of struc- groups in GO.
tural properties of GO and GO@f-SiO @Co (Fig. 5). Two charac- To show the efficiency of the catalyst, we tested its potential
teristic peaks for graphene oxide at 1595 cm (in-plane vibrations in the model reaction. For this purpose, different parameters
of the catalyst and related to the decomposition of functional
45
2
ꢁ1
2
ꢁ1
of sp bonded carbon) and 1338 cm (out of plane vibrations) such as solvents, variety of catalysts, time, and the amount of
were related to G and D bands, respectively. The Raman spectrum the desired catalyst were evaluated on the model reaction.
2
Fig. 5 The Raman spectra for GO and f-SiO @GO@Co.
2
Fig. 6 The TGA analysis for f-SiO @GO@Co.
©
2021 The Author(s). Published by the Royal Society of Chemistry
RSC Adv., 2021, 11, 17108–17115 | 17111

View Article Online
RSC Advances
Paper
a
Table 1 The results of different catalysts on the model reaction
Table 3 Evaluation of catalyst loading for upgrading the yield of the
reaction
a
b
c
Entry
Catalyst
Time
Yield (%)
b
c
Entry
Catalyst loading
Time
2 h
Yield (%)
1
2
3
4
5
6
7
—
NiO NPs
SiO
NiO@SiO
f-SiO
f-SiO
f-SiO
20 h
7 h
3 h
3 h
1 h
—
40%
60%
52%
70%
85%
98%
1
2
3
4
5
5
10
15
20
30
62%
74%
85%
98%
98%
2
NPs
90 min
45 min
5 min
5 min
2
NPs
2
2
2
@Fe
@GO
@GO@Co
3
O
4
30 min
5 min
a
Reaction conditions: 2-hydroxynaphthoquinone (1 mmol), 4-
a
Reaction conditions: 2-hydroxynaphthoquinone (1 mmol), 4- nitrobenzaldehyde (1 mmol), 3-nitro aniline (1 mmol), f-
b
nitrobenzaldehyde (1 mmol), 3-nitro aniline (1 mmol), different SiO @GO@Co different amounts, RT. stirring. Reaction progress
2
b
c
catalysts (20 mg), RT. stirring. Reaction progress monitored by TLC. monitored by TLC. Isolated yield.
c
Isolated yield.
In order to display the superiority of the catalyst, different Table 4 Synthesis of aminonaphthoquinone derivatives by f-SiO @-
2
GO@Co as a catalyst
catalysts were compared to a model reaction (4b). First, the
reaction was performed without the catalyst and no product was
formed aer 20 h (Table 1, entry 1). Then, different nano-
Entry Aldehyde
Amine Product Time (min) Yield (%)
particles were used and the obtained yield was checked. The
1
2
3
4
5
6
7
8
9
1
1
1
4-Cl
4-NO
2
3-OH
3-NO
2-OH
4-CH
Ph
2-OH-5-Br
4-OCH
4-N(CH
4-NO
3-NO
4-NO
3-NO
4-NO
4-NO
4-NO
4-NO
4-NO
4-NO
2
2
2
2
2
2
2
2
2
2
2
2
4a
4b
4c
4d
4e
4f
4g
4h
4i
5
5
7
7
8
7
6
6
7
7
7
5
98%
98%
96%
97%
96%
96%
96%
96%
96%
96%
95%
96%
nanoparticles resulted in low yield. Functionalized SiO
2
was
then used on Fe O and graphene oxide support. The obtained
3
4
2
result showed that graphene oxide was a better support with
more activity. Finally, f-SiO @GO and f-SiO @GO@Co were
2
2
3
2
compared. f-SiO @GO@Co resulted to have more acidic sites
and better catalytic efficiency with the maximum yield (98%) in
a minimum time (Table 1, entry 7).
In continuation, different protic (ethanol, water, and ethanol/
water) and aprotic (acetonitrile, THF, and toluene) solvents were
3
0
1
2
3
)
2
4j
4k
4l
3,4-Dimethoxy 4-NO
2-NO 4-NO
2
tested in the presence of f-SiO @GO@Co (20%) as a catalyst. The
2
results indicated that the reaction in the presence of protic
solvents was faster than that in the presence of aprotic solvents
and the nal yields ranged between 87% and 98%. The best protic
solvent was ethanol, which resulted in 98% yield of appropriate
product in minimum reaction time (Table 2, entry 2).
conditions for the reaction, aminonaphthoquinone derivatives
in the presence of the catalyst (20%) at room temperature in
ethanol were synthesized (Table 4).
2
Then, the effect of 10 and 20% (w/w) f-SiO loading on the GO
surface was evaluated. The result indicated that 20% (w/w) f- 3.2. Reusability of the catalyst
SiO2 on the surface of GO increases the catalyst's efficiency.
The reusability of the catalyst was examined by conducting the
recyclability test in the model reaction (4b). The catalyst was
separated at the end of the reaction by centrifugation and
Then, the impact of f-SiO @GO@Co amount in the reaction was
evaluated (Table 3, entries 1–5). The obtained result exhibited
that the catalyst loading of 20 wt% increased the yield up to 98%
2
(Table 3, entry 4) while loading higher than 20 wt% did not have
any impact on improving the yield. Aer nding the best
a
Table 2 Evaluation of different solvents on the model reaction
b
c
Entry
Solvent
Time
Yield (%)
1
2
3
4
5
6
THF
Ethanol
Water
Ethanol/water
Toluene
Acetonitrile
150 min
5 min
50 min
50 min
200 min
90 min
42%
98%
87%
92%
30%
42%
a
Reaction conditions: 2-hydroxynaphthoquinone (1 mmol), 4-
@GO@Co
20%), different solvents, RT. stirring. Reaction progress monitored
nitrobenzaldehyde (1 mmol), 3-nitroaniline (1 mmol), f-SiO
(
by TLC. Isolated yield.
2
b
c
2
Fig. 7 Recycling results of f-SiO @GO@Co on the model reaction.
17112 | RSC Adv., 2021, 11, 17108–17115
© 2021 The Author(s). Published by the Royal Society of Chemistry

View Article Online
Paper
RSC Advances
washed with ethyl acetate to remove impurities. The catalyst
was used six times with a great average recycling value (95%).
The results showed that the catalytic activity decreased from
98% in the rst run (fresh) to 89% aer the completion of the
sixth run (Fig. 7).
3.3. Analysis and characterization of the synthesized
compound
All the synthesized compounds (4a–l) were characterized with
1
13
different methods such as FT-IR and H NMR and C NMR
spectroscopy. The IR spectrum of the selected compound (4d)
ꢁ
1
shows peaks at 3388 and 3312 cm , which were related to OH
and NH symmetric stretching vibrations. The band at
1
13
Fig. 8 FT-IR, HNMR, CNMR spectra of compound 4d.
Scheme 2 A proposed mechanism for the synthesis of amino-
naphthoquinone derivatives.
2
Table 5 Comparison of the catalytic potential of f-SiO @GO@Co with previously reported catalysts for the synthesis of aminonaphthoquinone
Entry
Catalyst
Solvent
Ethanol
Temperature
Time
Yield (maximum)
Ref.
1
2
3
4
5
Montmorillonite-k10
PPA
r.t.
Ambient
Reux
Ambient condition
8 h
6 h
6.5 h
3 h
5 min
93
87.9
91
93
98%
46
47
48
49
H
H
2
O
O
InCl
g-Fe
f-SiO2@GO@Co
3
2
2
O
3
/SiO
2
-propyl-NH-AMAM-SO
3
H
Solvent-free
Ethanol
r.t.
This work
©
2021 The Author(s). Published by the Royal Society of Chemistry
RSC Adv., 2021, 11, 17108–17115 | 17113

View Article Online
RSC Advances
Paper
ꢁ
1
1
1
642 cm was for C]O stretching vibration (Fig. 8a). The H
I. A. Aksay, R. K. Prud'Homme and L. C. Brinson, Nat.
Nanotechnol., 2008, 3, 327–331.
NMR spectrum of compound 4d exhibited a single character-
istic peak at d ¼ 6.17 ppm for the CH group. The D O
4 Q. Yang, X. Pan, K. Clarke and K. Li, Ind. Eng. Chem. Res.,
2012, 51, 310–317.
2
exchangeable protons of amine and hydroxyl were observed in
1
3
the region of 7–8.30 ppm (Fig. 8b). The CNMR spectrum of
compound 4d showed a prominent peak at around 50.55 ppm,
which was related to the CH group and the peaks at 185 ppm
and 181 ppm correspond to the carbonyl groups (Fig. 8c).
5 U. K. Sur, Int. J. Electrochem., 2012, 2012, 1–12.
6 Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts and
R. S. Ruoff, Adv. Mater., 2010, 22, 3906–3924.
7 F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini,
A. C. Ferrari, R. S. Ruoff and V. Pellegrini, Science, 2015,
347, 1246501.
3.4. Proposed mechanism
8
S. C. Ray, Application and Uses of Graphene Oxide and Reduced
Graphene Oxide, Elsevier Inc., 2015.
B. Aday, H. Pamuk, M. Kaya and F. Sen, J. Nanosci.
Nanotechnol., 2016, 16, 6498–6504.
According to the proposed mechanism presented in Scheme 2,
aromatic amines react with activated benzaldehyde in the
presence of the catalyst through nucleophilic attack to form
activated imine as an intermediate(I). Then, the intermediate(I)
is attacked by 2-hydroxynaphthalene-1,4-dione through inter-
molecular H-atom transfer and nucleophilic addition, which
gives intermediate(II) and will undergo tautomerization to form
the nal products.
9
1
1
1
0 S. Bozkurt, B. Tosun, B. Sen, S. Akocak, A. Savk,
M. F. Ebeo ˘g lugil and F. Sen, Anal. Chim. Acta, 2017, 989,
88–94.
1 M. D. P. Lavin-Lopez, A. Romero, J. Garrido, L. Sanchez-Silva
and J. L. Valverde, Ind. Eng. Chem. Res., 2016, 55, 12836–
12847.
3
.5. Comparison of the performance of f-SiO @GO@Co with
2
2 R. Hajian, K. Fung, P. P. Chou, S. W. Wang and
some previously reported heterogenous catalysts
K. A. Balderston, Mater. Matters, 2019, 14, 37–45.
Comparative tests were performed to check the ability of f- 13 D. Chen, H. Feng and J. Li, Chem. Rev., 2012, 112, 6027–6053.
SiO @Go@Co as opposed to other previously reported catalysts 14 S. R. Chaurasia, R. Dange and B. M. Bhanage, Catal.
2
in the literature to synthesise aminonaphthoquinone. The
results revealed that f-SiO @Go@Co had a better catalytic 15 A. Dandia, S. Bansal, R. Sharma, K. S. Rathore and V. Parewa,
Commun., 2020, 137, 105933.
2
performance than the other catalysts in terms of yield and
RSC Adv., 2018, 8, 30280–30288.
production time (Table 5, entry 5).
16 A. Vijay Kumar and K. Rama Rao, Tetrahedron Lett., 2011, 52,
5188–5191.
1
7 Z. Li, R. Wang, R. J. Young, L. Deng, F. Yang, L. Hao, W. Jiao
and W. Liu, Polymer, 2013, 54, 6437–6446.
4
. Conclusion
GO@f-SiO @Co is a heterogenous catalyst synthesized with 18 T. Jiang, T. Kuila, N. H. Kim, B. C. Ku and J. H. Lee, Compos.
2
spherical silica particles graed on the surface of graphene
oxide with the help of ethylenediamine ligand and coordination 19 Y. J. Wan, L. X. Gong, L. C. Tang, L. Bin Wu and J. X. Jiang,
with Co(II). The activity of the catalyst for the synthesis of ami-
Composites, Part A, 2014, 64, 79–89.
nonaphthoquinones has been assessed. The results showed 20 D. Vennerberg, Z. Rueger and M. R. Kessler, Polymer, 2014,
Sci. Technol., 2013, 79, 115–125.
that the catalyst with high catalytic activity gave excellent yield
55, 1854–1865.
under mild conditions in a short reaction time.
21 X. Wang, W. Xing, P. Zhang, L. Song, H. Yang and Y. Hu,
Compos. Sci. Technol., 2012, 72, 737–743.
2
2 S. Z. Haeri, B. Ramezanzadeh and M. Asghari, J. Colloid
Interface Sci., 2017, 493, 111–122.
Conflicts of interest
There are no conicts to declare.
23 X. Shi, T. A. Nguyen, Z. Suo, Y. Liu and R. Avci, Surf. Coat.
Technol., 2009, 204, 237–245.
2
4 T. Wang, H. Ge and K. Zhang, J. Alloys Compd., 2018, 745,
Acknowledgements
705–715.
We are very grateful to the Kashan University for the nancial 25 A. N. Banerjee, Interface Focus, 2018, 8, 20170056.
support to run this project.
26 V. Georgakilas, J. A. Perman, J. Tucek and R. Zboril, Chem.
Rev., 2015, 115, 4744–4822.
2
7 M. Alvand and F. Shemirani, Microchim. Acta, 2017, 184,
References
1621–1629.
1
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, 28 N. Seifvand and E. Kowsari, RSC Adv., 2015, 5, 93706–93716.
S. V. Dubonos, I. V. Grigorieva and A. A. Firsov, Science, 2004, 29 R. J. R. Lumby, P. M. Joensuu and H. W. Lam, Org. Lett.,
06, 666–669. 2007, 9, 4367–4370.
X. Wang, L. Zhi and K. M u¨ llen, Nano Lett., 2008, 8, 323–327. 30 J. Wang, K. Feng, H. H. Zhang, B. Chen, Z. J. Li, Q. Y. Meng,
3
2
3
T. Ramanathan, A. A. Abdala, S. Stankovich, D. A. Dikin,
M. Herrera-Alonso, R. D. Piner, D. H. Adamson,
H. C. Schniepp, X. Chen, R. S. Ruoff, S. T. Nguyen,
L. P. Zhang, C. H. Tung and L. Z. Wu, Beilstein J.
Nanotechnol., 2014, 5, 1167–1174.
17114 | RSC Adv., 2021, 11, 17108–17115
© 2021 The Author(s). Published by the Royal Society of Chemistry

View Article Online
Paper
RSC Advances
3
1 J. M. Khurana, A. Lumb, A. Chaudhary and B. Nand, Synth. 40 X. H. Yau, F. W. Low, C. S. Khe, C. W. Lai, S. K. Tiong and
Commun., 2013, 43, 2147–2154. N. Amin, PLoS One, 2020, 15, 1–15.
2 A. Feitosa Dos Santos, P. A. L. Ferraz, A. Ventura Pinto, 41 I. Calizo, A. A. Balandin, W. Bao, F. Miao and C. N. Lau, Nano
3
M. D. C. F. R. Pinto, M. O. F. Goulart and
A. E. G. Sant'Ana, Int. J. Parasitol., 2000, 30, 1199–1202.
3 J. Chen, Y. W. Huang, G. Liu, Z. Afrasiabi, E. Sinn, S. Padhye
and Y. Ma, Toxicol. Appl. Pharmacol., 2004, 197, 40–48.
4 S. Gafner, J. L. Wolfender, M. Nianga, H. Stoeckli-Evans and
K. Hostettmann, Phytochemistry, 1996, 42, 1315–1320.
5 J. E. Kuder, D. Wychick, R. L. Miller and M. S. Walker, J. Phys.
Chem., 1974, 78, 1714–1718.
Lett., 2007, 7, 2645–2649.
42 K. N. Kudin, B. Ozbas, H. C. Schniepp, R. K. Prud'homme,
I. A. Aksay and R. Car, Nano Lett., 2008, 8, 36–41.
43 P. A. Mikhaylov, M. I. Vinogradov, I. S. Levin and
G. A. Shandryuk, Mater. Sci. Eng., 2019, 693, 012036.
44 S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas,
A. Kleinhammes, Y. Jia, Y. Wu, S. B. T. Nguyen and
R. S. Ruoff, Carbon, 2007, 45, 1558–1565.
3
3
3
3
6 A. Esteves-Souza, K. Ara u´ jo L u´ cio, A. S. da Cunha, A. da 45 Y. Huang, W. Yan, Y. Xu, L. Huang and Y. Chen, Chem. Synth.
Cunha Pinto, E. L. da Silva Lima, C. A. Camara, Appl. Graphene Carbon Mater., 2016, 43–52.
M. Domingues Vargas and C. R. Gattass, Oncol. Rep., 2008, 46 S. Jayashree and K. Shivashankar, Synth. Commun., 2018, 48,
0, 225–231. 1805–1815.
7 T. M. S. Silva, C. A. Camara, T. P. Barbosa, A. Z. Soares, 47 D. Liu, S. Zhou and J. Gao, Synth. Commun., 2014, 44, 1286–
2
3
L. C. Da Cunha, A. C. Pinto and M. D. Vargas, Bioorg. Med.
Chem., 2005, 13, 193–196.
8 V. K. Tandon, D. B. Yadav, R. V. Singh, A. K. Chaturvedi and
1290.
48 M. Dabiri, Z. N. Tisseh and A. Bazgir, Dyes Pigm., 2011, 89,
63–69.
3
P. K. Shukla, Bioorg. Med. Chem. Lett., 2005, 15, 5324–5328. 49 F. Mollazehi and H. R. Shaterian, Appl. Organomet. Chem.,
9 S. Siddiqui and Z. N. Siddiqui, Nanoscale Adv., 2020, 2, 4639– 2018, 32, 1–10.
651.
3
4
©
2021 The Author(s). Published by the Royal Society of Chemistry
RSC Adv., 2021, 11, 17108–17115 | 17115