Ionic Liquid Supported on DFNS Nanoparticles Catalyst in Synthesis of Cyclic Carbonates by Oxidative Carboxylation

Article abstract of DOI:10.1007/s10562-021-03616-6

In this paper, in the proximity of epoxides, we have suggested the conversion of carbon dioxide (CO₂) for cyclic carbonates known as the most proper approach for synthesizing this C1 building block. Oxidation carboxylation of styrenes with CO₂ is performed at aerobic conditions utilizing the present approach. Oxidize carboxylation of styrenes by CO₂ was performed in the presence of DFNS-IL as NPs. Good to superb performance products were provided deploying DFNS-IL nanocatalyst. In addition, the anatomy of DFNS-IL has been distinguished by various methods, including XRD, VSM, FT-IR, SEM, EDX, TEM, and TGA. The stability of the catalytic system increased after the excessive addition of DFNS. In addition, the hot filtration test provided complete insight into the heterogeneity of the catalyst. The reuse and recycling of the catalyst were repeatedly investigated for coupling reactions. In addition, the mechanism of the coupling reactions was thoroughly studied. Graphic Abstract: Ionic liquid supported on DFNS nanoparticles catalyst in synthesis of cyclic carbonates by oxidative carboxylation [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-021-03616-6

Catalysis Letters
https://doi.org/10.1007/s10562-021-03616-6
Ionic Liquid Supported on DFNS Nanoparticles Catalyst in Synthesis
of Cyclic Carbonates by Oxidative Carboxylation
Mengbing Cui · Farzaneh Shamsa2
1
Received: 3 January 2021 / Accepted: 28 March 2021
©
The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2021
Abstract
In this paper, in the proximity of epoxides, we have suggested the conversion of carbon dioxide (CO ) for cyclic carbonates
2
known as the most proper approach for synthesizing this C1 building block. Oxidation carboxylation of styrenes with CO
2
is performed at aerobic conditions utilizing the present approach. Oxidize carboxylation of styrenes by CO was performed
2
in the presence of DFNS-IL as NPs. Good to superb performance products were provided deploying DFNS-IL nanocatalyst.
In addition, the anatomy of DFNS-IL has been distinguished by various methods, including XRD, VSM, FT-IR, SEM, EDX,
TEM, and TGA. The stability of the catalytic system increased after the excessive addition of DFNS. In addition, the hot
ꢀ
ltration test provided complete insight into the heterogeneity of the catalyst. The reuse and recycling of the catalyst were
repeatedly investigated for coupling reactions. In addition, the mechanism of the coupling reactions was thoroughly studied.
Graphic Abstract
Ionic liquid supported on DFNS nanoparticles catalyst in synthesis of cyclic carbonates by oxidative carboxylation
Ionic liquid supported on DFNS nanoparticles catalyst in
synthesis of cyclic carbonates by oxidative carboxylation
O O
Si
O
Cl
-
N
N
Br
-
Br
-
N
N
Cl
-
Si
O
O O
O
O
O
+
[O] + CO
2
R
R
Keywords Nanocatalyst · Green chemistry · Carbon dioxide · Ionic liquids · DFNS
1
Introduction
*
*
Mengbing Cui
cuimengbing@163.com
The proper organic chemicals can be obtained by converting
carbon dioxide known as a promising research area [1–5].
There organic chemicals are not a greenhouse gas emis-
sion or a waste material produced in chemical industries
but also a non-ꢁammable, non-toxic and readily available
carbon raw material [6, 7]. However, in the conversion of
Farzaneh Shamsa
Farzaneh.Shamsa@gmail.com
1
2
College of Pharmacy, Xinxiang University,
Xinxiang 453003, China
New Materials Technology and Processing Research Center,
Department of Chemistry, Neyshabur Branch, Islamic Azad
University, Neyshabur, Iran
CO molecules, thermodynamically, they are not utilized in
2
Vol.:(0
1
123456789)
3

M. Cui, F. Shamsa
the industry due to the fact that CO possesses low reactivity,
ꢀber (number of ꢀbers into one sphere), the DFNS outer
2
2
−1
high active catalysts, energy inputs, optimization conditions,
layer area may alter from 450 to 1244 m g [29]. It should
be noted that unlike the erratic distribution of pores in usual
silica materials, DFNS has oriented ꢀbrous channels that
increase in size from the center to the external layer. Control-
ling DFNS ꢀber density can adjust the volume and size of
the pores. Its adjustable pore size in the range of 3.7–25 nm
allows pores to ꢀt the particular visitant molecules in diꢂer-
etc. known as key factors [8].
In diꢂerent industries, cyclic carbonates were widely used
as electrolytes in intermediate organic synthesis, monomers,
aprotic polar solvents and lithium batteries. In the recent
years, many cyclic carbonate combinations were produced
from CO . Among them, the cycloaddition of CO to epox-
2
2
3
−1
ides was determined as a usual and industrial method [9,
ent sizes, whilst its adjustable pore volume of 2.18 cm g
1
0]. Because of the simply available and lower cost raw
facilitates the high loadings of visitants [30, 31]. Visitants
include organometallic complexes, organic molecules,
metals, inorganic salts, peptides, metal oxides, enzymes,
proteins, carbon, and polymers. The integrated porosity of
DFNS accompany with its hierarchical pore arrangement
including mesopores of various sizes (such as suitable
amounts of macr- and microopores) helps the visitant mol-
ecules to eꢃciently adsorb and diꢂuse in the ꢀbrous spheres
with minimal constraints; it helps to increase the accessibil-
ity of active sites and the internallayer (a signiꢀcant issue in
usual mesoporous materials). Macropores contribute to the
eꢂective initial diꢂusion/adsorption of guest molecules and
DFNS have proper stability (mechanical, chemical, hydro-
thermal, and thermal) toward usual mesoporous materials,
which is a major concern due to their thin silica walls. DFNS
is biocompatible as well as nontoxic. Particle size control
facilitates partial modiꢀcation of dispersion and realization
of these nanospheres.
materials, alkenes as well as do not require the separation
of epoxide, after the ꢀrst step, direct production of cyclic
carbonates from CO and also oleꢀns using oxidative car-
2
boxylation (refer to Scheme 1) consists a mixture of alkene
epoxidation and CO cycloaddition to epoxide production
2
can be a more cost eꢂective method [11–18]. Oleꢀn oxida-
tive carboxylation has been explored in 1962 but more stud-
ies on the cycloaddition of CO to epoxide ring still require
2
further studies [19–21].
As for morphology-controlled nanomaterials, dendritic
ꢀ
brous nanosilica has been recently discovered by Polshet-
tiwar et al. [22–24]. It depicted exceptional activities in
all areas, including gas adsorption, catalysis, energy stor-
age, solar-energy harvesting, biomedical applications and
sensors. It is called dendrimeric silica ꢀbers morphology
(
DFNS) considering the ꢀbrous morphology reported in our
previous report [25–28]. Since the ꢀbers were thin sheets
.5–5.2 nm thick, other names are deployed in the literature,
3
Dendrimers are popular in the domain of catalysis
because of highly branched 3D anatomies, unique dendritic
eꢂects, and numerous peripheral categories [32, 33]. Immo-
bilizing the dendrimer catalyst on support materials has
attracted the attention of many chemists due to facile reus-
ability and recoverability [34–36]. ILs have been extensively
utilized in green chemistry due to their speciꢀc characteris-
tics, including low vapor pressure, low burnability, ꢀrmness,
etc. The ability to adjust anatomy and characteristics is the
most signiꢀcant property of ILs. The physical and chemical
characteristics of ILs can be adjusted by introducing vari-
ous functional groups into anions or cations with diverse
anatomies. Dendritic ILs (DILs), which are a combination of
the characteristics of dendrimers and ILs, have extensively
including wrinkled, ꢀbrous, dendritic, nanoꢁower, lamel-
lar, and dandelion. In this study, to prevent confusion, we
used the name employed in the respective original works.
However, to maintain consistency, we use dendritic ꢀbrous
nanosilica as a common name for this family of materials.
The uniform roots of DFNS roots in their dendritic ꢀbrous
morphology are more accessible in all dimensions and sides
in comparison with the tubular pores of SBA-15 and MCM-
4
1. This ꢀbrous structure increases the active sites like metal
oxides, metals, organic molecules, and organometallics in
the outer layer of silica without blocking the channels. In
addition, it allows more access to generated active sites. By
modifying the particle size (40–1120 nm) and density of
O
O
O
DFNS-IL
+
[O] + CO2
R
R
Scheme 1 Synthesis of cyclic carbonates through oxidative carboxylation of alkenes
1
3

Ionic Liquid Supported on DFNS Nanoparticles Catalyst in Synthesis of Cyclic Carbonates by…
utilized in the domain of catalysis, transporters, and adsorp-
tion of heavy metal cations [37, 38].
2.4 Synthesis of DFNS‑IL Catalyst
The current study reports the novel green approach for
the synthesis of DFNS NPs immobilized by ILs based on
First, DFNS was sonicated in toluene (15 ml) for 40 min.
The provided ionic liquid (3.0 mmol) was then released and
the reaction was continued for 68 h under reꢁux situations.
Upon completion, the resulting precipitate was isolated
employing an external magnet and washed with 15 ml of
ethanol to eliminate the unreacted ionic liquid. The result-
ing solids were dried at r.t. and employed as the catalyst in
providing quinazolinone derivatives.
1
,4-diazabicyclo[2.2.2]octane (DABCO), as DABCO is a
medium-hindrance tertiary amine with cage-like anatomy.
This anatomy was utilized as a cheap, green, highly reꢁex-
ive, and non-poisonous catalyst for diꢂerent ionic liquids.
The ꢀndings illustrated the inꢁuence of IL on the nano anat-
omies and characteristics. This catalyst has many advan-
tages, including facile separation, good activity, and selec-
tivity for oxidation carboxylation of styrenes by using CO
2.5 Catalytic Reactions
2
under mild conditions (refer to Scheme 1).
The related reaction was done into a stainless autoclave (by
the volume of 25 mL). Twenty millimole oleꢀn, and 10 mg
DFNS-IL were used in the stainless autoclave. The obtained
compound was then stirred utilizing a magnetic stirrer. After
that, it was laced in a water bath and was heated to the appro-
priate temperature. For many times, reactor was purged by
CO and charged by CO . After that, the stainless autoclave
2
Experimental
2.1 A Universal Approach for Providing DFNS
Nanoparticles
2
2
Tetraethyl orthosilicate (TEOS) (3.5 g) was dissolved in a
solution of cyclohexane (40 mL) and 1-pentanol (3.0 mL).
Then, a mixed solution of cetylpyridinium bromide (CPB)
was heated to an appropriate temperature and stirred for a
half of hour. After the reaction was ꢀnished, the reactor is
then cooled to the temperature of 25 °C, and the remained
(
1.5 g) and urea (0.9 g) in H O (45 mL) was released and
CO was slowly discharged from the reactor. The obtained
2
2
continually mixed for 45 min at room temperature. Next,
it was located in a Teꢁon-sealed hydrothermal reactor and
heated at 130 °C for 3 h. The generated silica was centri-
fuged then washed with a mixture of deionized water and
acetone, and oven-dried. The material was then calcined in
air at 600 °C for 6 h.
solution from the reaction was evaluated using GC–MS and
GC.
3 Results and Discussion
The synthesis of DFNS-IL NPs was a multi-step process.
The ꢀbers of DFNS has several Si–OH groups on the outer
layers. Therefore, the DFNS rapidly functionalized with
3-chloropropyltriethoxysilane and produced DFNS/3-
chloropropylsilane NPs. Then, with DABCO support on
DFNS/3-chloropropylsilane nanoparticles, DFNS-IL cata-
lyst was synthesized in a simple and cheap procedure that
is characterized by easy access to active sites and high
catalytic activity (Scheme 2).
2
.2 A Universal Approach for Providing
DFNS/3‑chloropropyltriethoxysilane
Nanoparticles
A solution of 3 mmol of DFNS NPs and 30 mL tetrahy-
drofuran was made in a beaker, and then 30 mmol of NaH
was released by ultrasonication. 30 mmol 3-chloropropyltri-
ethoxysilane was dispersed drop-wise at r.t. and mixed for
another 13 h at 75 °C. The ꢀnal products were washed with
ethanol and deionized water, respectively, and vacuum-dried
at 60 °C for 2 h.
The anatomies of the synthesized DFNS, and DFNS-
IL NPs were investigated by SEM and TEM. The DFNS
microspheres with ꢀbrous anatomy were identical and
monodispersed (Fig. 1a). The average diameter of the
microspheres was about 200–250 nm. TEM and SEM pic-
tures (Fig. 1a and c) further illustrate that the two ꢀbers
were approximately 10–20 nm apart. The SEM pictures of
DFNS-IL NPs show that rectiꢀcation did not change the
morphology of DFNS (Fig. 1b and d); however, discrete
nanospheres grew as twins.
2.3 Synthesis of 4,40‑(butane‑1,4‑diyl)
bis‑1,4‑diazabicyclo[2.2.2]octane‑1,4‑diium(IL)
A blend of ethylacetate (15 ml),1,4-dibromobutane
(
(
3.0 mmol) and 1,4-diazabicyclo[2.2.2]octane (DABCO)
7 mmol) were mixed at r.t. for 20 h. The white precipi-
tate was isolated, suspended in 15 ml of anhydrous tetrahy-
drofuran, and stirred at 30 °C. After 2 h, the solvent was
eliminated by centrifugation and the solid was dried at room
temperature (melting point of ionic liquid=247–249 °C).
FT-IR spectroscopy was deployed to discover the
changes in the level of the synthesized catalyst (Fig. 2).
−
1
The bands at 799, 1086, and 1662 cm in the FT-IR
spectrum of both DFNS and DFNS-IL corresponds to the
1
3

M. Cui, F. Shamsa
tensile state of typical silanol group (Si–OH), Si–O–Si
vibrations, and the water absorbed on the solid outer layer,
respectively (Fig. 2a and b). Robust absorption bands at
was speciꢀed by EDX analysis. Figure 5 illustrates the ele-
ments in DFNS-IL NPs such as nitrogen, silicon, oxygen,
carbon, chlorine, and bromine. The NPs outer layer rough-
ness was determined by atomic force microscopy (AFM)
analysis. Figure 6 illustrates the topographic scheme. The
higher altitude region, shown in bright yellowish white, was
increased by reducing T/W. This indicated an enhancement
in the unevenness of the catalyst’s outer layer.
−
1
1
615 and 1458 cm were diꢂerentiated from C–N and
C–C vibrations of the DABCO section. The absorp-
tion bands were related to the different (C–H) bonds
like N–CH , CH –CH and C–H emerged at 2896, 2972,
2
2
2
−
1
3
062 cm . These observations aꢃrmed that the silica-
coated outer layer of the DFNS was strongly altered with
the 4,40-(butane-1,4-diyl)bis-1,4-diazabicyclo[2.2.2]
octane-1,4-diium) as ionic liquids.
Nitrogen adsorption–desorption isotherm analysis was
performed to investigate the particular outer layer area and
porosity of the products. Following the BJH approach, the
mean pore diameter, the particular outer layer area, and
the total pore volume values were determined (Table 1).
The BET ꢀndings illustrated that the active outer layers of
Figure 3 shows the TG analysis of DFNS-IL NPs. The
TG curve of DFNS-IL NPs illustrated weight reduction at
7
0 °C to 280 °C, which corresponded to the water molecules
2
−1
adsorbed in the support. The organic group functionalized
analogs DFNS-IL experienced notable weight loss (32%)
at~400 °C, possibly because of ligand decomposition.
We utilized XPS to examine the chemical sections on the
DFNS-IL NPs level. Figure 4 shows a scheme of XPS for the
gathered catalyst. Peaks Cl, C, O, N, and Br can be seen and
the attendance of N 1 s additional aꢃrms that DFNS were
functionalized employing DABCO. In addition, the presence
the DFNS and DFNS-IL are 632 and 309 m g , respec-
tively. The results demonstrated that the specific outer
layer reduced after DABCO intercalation. Moreover, the
pore volume and average pore radius reduced by employ-
ing DABCO. DABCO intercalation was found to have more
porous network anatomy.
Impressive elements like the catalyst amount, oxidant and
solvent for the oxidation carboxylation of styrenes with CO
2
−
of ions of Br (the DABCO counter ion) was determined by
known as a model reaction are investigated for obtaining
the optimum conditions in terms of the oxidation reactions.
Many solvents are utilized for studying the related eꢂect
an edged apex. This shows the presence of DABCO in the
catalyst. Figure 5 illustrates the origins of the catalyst that
O
O
Si
OEt
O
EtO
EtO Si
EtO
Cl
Cl
Cl
EtO
Si
OEt
OEt
O Si
O
O
DFNS
DFNS
Br-
N
N
N
Br-
N
O
Br-
Cl-
N
O
O Si
O
N
-
N
Br-
N
Si O
Cl
O
Br-
N
N
Br
+
Br
N
N
Br-
N
N
Scheme 2 Preparation of DFNS-IL nanocatalyst
1
3

Ionic Liquid Supported on DFNS Nanoparticles Catalyst in Synthesis of Cyclic Carbonates by…
Fig. 1 TEM pictures of a
DFNS and b DFNS-IL NPs;
SEM pictures of c DFNS and d
DFNS-IL NPs
onto the production of cyclic carbonates and no considerable
product is synthesized by polar protic solvents like 2-pro-
panol, methanol, ethanol and water. Polar protic solvents
like EtOAc, DMSO, and DMF demonstrated mild eꢃciency
in cross-coupling products. It is found that solvents are less
eꢃcient compared to usual heating under solvent-free states.
The cross-coupling reaction performance of carbonylation
is higher in less polar solvents like toluene or anisole. A
constant amount of catalyst (10.0 mg) is enough to obtain
the quantitative performance of product. Lower amounts
obtained in lower yields. The signiꢀcance and the inꢁuence
of the catalyst is proved while the reaction at the existence of
the catalyst demonstrated no eꢃciency. Noted that, cases of
all reactions, a selectivity of more than average 99% to prod-
uct is archived. The selective production of cyclic carbonate
demonstrated the highest eꢃciency for around 25 min at
and 1.0 MPa. Based on previous studies, it is found that
the enhancement of reaction pressure until the pressure is
under 1.0 MPa is determined very favorable in the case of
cyclic carbonate production. Hence, 1.0 MPa CO pressure
2
is speciꢀed as a special condition. For increasing yields
of product, many oxidants are utilized. The yield of reac-
tion is dramatically sensitive to the oxidant. Noted that, the
basicity of catalyst is not known as a parameter for specify-
ing activity. As can be seen in Table 3, the highest yield is
determined by utilizing oxygen as an oxidant. In addition,
the production of cyclic carbonate enhanced around 99%
under the temperature of 60 °C and 1.0 MPa CO pressure
2
at 25 min. It should be noted that more enhancement in tem-
perature caused in a low reduction in the yields of the prod-
uct because of an insigniꢀcant value of speciꢀc byproducts
like oleꢀn isomerization. Hence, in the case of the parallel
2
5 °C under an open air atmosphere. In Table 2, there are not
reactions of oleꢀn and CO , the optimum temperature is
2
oxidants of additives in the case of this conversion.
determined to be 60 °C.
The pressure of CO possessed a considerable impact on
As can be seen in Table 4, in this novel one-pot approach,
many oleꢀns are studied in cases of the substrate scopes
to produce cyclic carbonates. Noted that, for all considered
2
the parallel reaction. Table 3 shows that the rate of reac-
tion rapidly enhanced considering the pressures among 0.5
1
3

M. Cui, F. Shamsa
Fig. 2 FTIR spectra of a DFNS; b DFNS-IL NPs
1
00
95
90
85
80
75
70
65
0
100
200
300
400
T/oC
500
600
700
800
Fig. 3 TGA diagram of DFNS-IL NPs
substrates, the catalyst is active. In addition, aryl oleꢀns
bearing a para-chloro group have been introduced as proper
substrates provided near-quantitative products. Aryl oleꢀns
and also the meta or ortho-chloro groups, are additionally
Fig. 4 XPS spectra of DFNS-IL NPs
1
3

Ionic Liquid Supported on DFNS Nanoparticles Catalyst in Synthesis of Cyclic Carbonates by…
Table 2 The eꢂect of solvent, amount of catalyst, time, and tempera-
ture for synthesis of cyclic carbonate
Entry
Solvent
Catalyst (mg)
Time (min)
Yield (%)a
1
2
3
4
5
6
7
8
9
EtOH
MeOH
i-PrOH
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
15
10
5
45
45
45
45
60
60
60
70
60
70
70
60
50
50
70
70
70
45
45
45
45
35
25
15
–
–
–
–
H O
2
DMF
THF
DMSO
Dioxane
31
42
79
–
47
54
58
18
79
–
13
20
22
99
99
99
92
99
99
73
CH CN
3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
CH Cl
2
2
EtOAc
Toluene
CHCl3
n-Hexane
Benzene
Fig. 5 EDX spectra of DFNS-IL NPs
CCl4
Cyclohexane
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
10
10
10
aGC yields [%]
Fig. 6 3D AFM cultivars of DFNS-IL NPs
Table 1 Anatomical parameters of DFNS, and the DFNS-IL NPs
Table 3 Eꢂect of oxidant, CO pressure, and temperature on the car-
2
2
boxylation of styrenes with CO
SBET (m2 g−1)
V (cm3 g−1)
Catalysts
DBJH (nm)
a
Entry
Oxidant
CO Pressure Temperature Yield (%)a
2
DFNS
DFNS-IL
632
309
3.0
1.2
13
7
(
MPa)
(°C)
1
2
3
4
5
6
7
8
9
O2
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.5
1.0
0.5
1.0
1.0
1.0
80
80
80
80
80
80
80
80
80
80
70
60
50
99
91
42
–
–
27
–
99
99
35
99
99
90
TBHP
H O
2
2
appropriate substrates. Whereas an electron-donating group
like methyl over the aryl group reduced the product yield.
For a deeper evaluation of the eꢃciency of the catalyst,
various control experiments were conducted and the results
are shown in Table 5. The reaction performed deploying
DFNS showed that no amount of the product was formed
after 25 min (Table 5, row 1). Moreover, no reaction was
perceived when DFNS/3-chloropropyl as catalyst was
employed (Table 5, row 2). 3-chloropropyl is not able to
show good catalytic activity under standard reactions. Due to
these unfavorable results, we continued research to increase
eꢃciency by adding IL (Table 5, row 3). Our results show
Oxone
KIO4
NaOCl
Air
O2
O2
O2
O2
O2
O2
10
11
12
13
aGC yields [%]
1
3

M. Cui, F. Shamsa
that the reaction cycle is primarily catalyzed using IL in the
DFNS nanostructure. Nanoparticles increase the activity of
the catalyst due to the increase in surface area to volume,
so they signiꢀcantly increase the sensitivity between the
reactants and the catalyst and act as a homogeneous catalyst
(Table 5, rows 3 and 4).
The catalytic activity of DFNS-IL NPs was compared
with other reported catalysts used for carboxylation of sty-
renes with CO (Table 6). Our outcomes proved that DFNS-
2
IL had the best performance of product in diꢂerent solvent,
temperature, and time, which conꢀrmed that our catalyst
was more active.
Table 4 Cycloaddition of CO with terminal oleꢀnsa
2
Entry
1
Oleꢀns
Products
Yield (%)
99
In green chemistry, the catalyst recyclability is known a
eꢂective characteristic. Hence, the MNPs of DFNS-IL recy-
clability is evaluated to synthesis the cyclic carbonate. After
the completion of the reaction, the solid MNPs of DFNS-IL
are removed simply from the liquid reaction area at only few
seconds, which can be recycled immediately after cleaning
the solvent. In Figs. 7, 10 runs in a row reuse of the catalyst
is shown. The eꢃciency of the product in the 10 th run is
determined equal to 98% that demonstrated merely a 6%
reduction with the eꢃciency of 92%.
2
3
94
96
We also performed a complete study on the catalyst het-
erogeneous nature. At ꢀrst step, the hot ꢀltration experi-
ment for production of cyclic carbonate is performed under
premium states and indicated that the catalyst is removed,
magnetically, in situ after near 73% (for around 15 min
removal). In order to tolerate more reaction, the reactants
were permissible. It is determined that the free catalyst
remnant determined to be fairly active, and 75% conversion
is detected after 25 min of the cyclic carbonate production
after removing the heterogeneous catalyst. We found that, in
the process of reaction, the catalyst heterogeneously worked
and unwilling just low leaching done in the reaction (Fig. 8).
The SEM and TEM image analysis illustrated the higher
numbers of the ꢀbrous nanoparticles of DFNS-IL. Fig-
ure 9a and b depict the SEM and TEM pictures of the new
4
5
6
92
97
99
ꢀ
brous nanoparticles of DFNS-IL, and the ten-times recy-
cled DFNS-IL. The ꢀbrous anatomy of the catalyst was still
visible after ten reuses and did not diꢂer from fresh nano-
particles after ten consecutive uses. This can be attributed
to strong recyclability. Moreover, the thermal stability of
the recycled DFNS-IL catalyst was not as good as the fresh
Table 5 Inꢁuence of diꢂerent
Yield (%)b
Entry Catalyst
catalysts for carboxylation of
a
styrenes with CO
2
1
2
DFNS
-
-
DFNS/3-
chloro-
propyl
3
4
DFNS-IL
IL
99
97
a
Reaction conditions: CO2
1.0 MPa), aniline (1.0 mmol),
(
and catalysts (10 mg), under
a
60 °C
Reaction conditions: appropriate CO (1.0 MPa), aniline (1.0 mmol),
2
b
DFNS-IL (10 mg), and under 60 °C.
Isolated yield
1
3

Ionic Liquid Supported on DFNS Nanoparticles Catalyst in Synthesis of Cyclic Carbonates by…
Table 6 Comparing the catalytic eꢃciency of DFNS-IL NPs to many catalystsa
Entry
Catalyst
Temp
Time (h)
Solvent
Yield (%)
1
2
3
4
Fe(III)@MOF1
50
65
50
100
24–48
30
96
DCM
TBHP
–
69 [39]
63 [40]
82 [41]
77 [42]
[C C Im][HCO ]
n
m
3
6
_
[ZnW O ]
1
2
40
Co(acac) -QPB@
10
MeCN
2
MCS
5
6
7
Ti-MMM-E
[Ru(TPP)(O)2]
70
30
100
48
48
6
–
49 [43]
53 [14]
32 [44]
DCM
MeCN
manganese(III)-
complex
8
9
NBS/DBU
DFNS-IL
60
60
3–6
1
H O
–
70 [45]
99
2
a
Reaction conditions: cycloaddition of CO in diꢂerent solvent, temperature, and time
2
1
00
90
80
70
60
50
40
30
20
10
0
1
2
3
4
5
6
7
8
9
10
Reuse
Fig. 7 The reusability of catalysts for synthesis of cyclic carbonate
Fig. 8 Reaction kinetics, and hot ꢀltration studies for synthesis of
cyclic carbonate
Fig. 9 a TEM and b FE-SEM
pictures of the improved DFNS-
IL NPs after the tenth run for
synthesis of cyclic carbonate
1
3

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Fig. 10 TGA of the fresh DFNS-IL catalyst (a) and the recycled
DFNS-IL catalyst after 10 times reusing (b)
catalyst after ten uses. This may be due to the loss of IL
in DFNS ꢀbers during recycling (Fig. 10). Fortunately, its
performance does not change at 100 °C.
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4
Conclusions
4
9:9652–9656
In summary, a novel class of DFNS was reported with sup-
port for ionic liquids based on ligands of DABCO groups,
which exhibits tremendous catalytic activity for provide
cyclic carbonate in excellent eꢃciency. SEM, TEM, FTIR,
XPS, ICP-MS, BET, TGA, and EDX indicated the func-
tionalization of IL in the outer layer of the mesopores silica.
Moreover, the catalyst was reusable and easily recover-
able. Such a logical design for single-site catalysts with full
employment of any IL active site, superb reusability, and
insigniꢀcant catalyst leaching are consistent with the con-
cepts of green chemistry. Therefore, the study of DFNS-IL
may create a potential basis for the fabrication of other read-
ily available nanocatalyst that would be robustly eꢃcient in
diꢂerent nanocatalyst-based reactions. This process might
lead to the production of nanocatalysts with desirable char-
acteristics, including eꢃciency and ease of reuse.
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