Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation of Carbon Dioxide with Epoxides by Using a Carbon Dioxide Balloon

Article abstract of DOI:10.1007/s10562-020-03135-w

Abstract: In the present study, the nanocatalyst of imidazolium based ionic liquids (ILs) is synthesized for the fixation of carbon dioxide (CO₂) under moderate conditions by utilizing a balloon of CO₂ with commercially available epoxides. IL incorporated porous dendritic fibrous nanosilica (DFNS) catalyst (IL/DFNS) was designed and synthesized. The synthesized catalyst was characterized using N₂ absorption desorption isotherm, XPS, SEM, EDX, TGA, HR-TEM, and AFM. For cyclic carbonate, an environmental friendly catalyst of porous IL/DFNS indicate highly impressive catalytic efficiency from CO₂ through CO₂ fixation and epoxides under mild condition. Attendance of polar hydroxyl and anion exchange nature groups of IL frame work to high surface area is known as the main aspect to be reliable for elevated catalytic efficiency and also advance in stability of catalyst and providing a proper recyclability. Graphic Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-020-03135-w

Catalysis Letters
https://doi.org/10.1007/s10562-020-03135-w
Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation
of Carbon Dioxide with Epoxides by Using a Carbon Dioxide Balloon
Pu Zhang1 · Rahele Zhiani2,3
Received: 16 December 2019 / Accepted: 1 February 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
In the present study, the nanocatalyst of imidazolium based ionic liquids (ILs) is synthesized for the fxation of carbon diox-
ide (CO2) under moderate conditions by utilizing a balloon of CO2 with commercially available epoxides. IL incorporated
porous dendritic fbrous nanosilica (DFNS) catalyst (IL/DFNS) was designed and synthesized. The synthesized catalyst was
characterized using N2 absorption desorption isotherm, XPS, SEM, EDX, TGA, HR-TEM, and AFM. For cyclic carbonate,
an environmental friendly catalyst of porous IL/DFNS indicate highly impressive catalytic efciency from CO2 through CO2
fxation and epoxides under mild condition. Attendance of polar hydroxyl and anion exchange nature groups of IL frame work
to high surface area is known as the main aspect to be reliable for elevated catalytic efciency and also advance in stability
of catalyst and providing a proper recyclability.
Graphic Abstract
Synthesis of ionic liquids as novel nanocatalysts for fixation of carbon
dioxide with epoxides by using a carbon dioxide balloon
O
C12
H
25 Cl-
Oi
OS
N
HN
HN
N
N
N
O
O
i
Cl-
S
O
C12H25
O
O
O
O
CO2
R
R
Keywords Nano catalyst · One-pot synthesis · Green chemistry · Carbon dioxide
1 Introduction
* Pu Zhang
Because of environmental convenience and sustainable
puzhanglvliang@sina.com
increasing from the usage of renewable sources and the
rising concentration of emissions, the CO2 exploitation, as
a green source of carbon for the manufacture of valuable
added chemical intermediates is garnered higher attention
in the recent studies [1–5]. Consequently, taking neces-
sary steps to control the emission of the industrial raw
materials by fue-gas capture and converting it to favora-
ble economically competitive products are important tasks
[2, 6–13]. In this regards, scholars across the globe are
* Rahele Zhiani
r_zhiani2006@yahoo.com
1
Department of Chemistry and Chemical Engineering,
Lvliang University, lvliang 033000, Shanxi, China
2
New Materials Technology and Processing Research Center,
Department of Chemistry, Neyshabur Branch, Islamic Azad
University, Neyshabur, Iran
3
Young Researchers and Elite Club, Neyshabur Branch,
Islamic Azad University, Neyshabur, Iran
Vol.:(0123456789)
1 3

P. Zhang, R. Zhiani
currently concerning for invention of novel protocols that
may properly capture the atmospheric CO2 and then con-
vert it to value-added substances [14–17]. However, there
are diferent challenges in the case of developing green
and highly efcient ways for CO2 fxation reaction under
green conditions [18–21].
O
C12H25
Oi
OS
Cl-
N
HN
HN
N
N
N
The organocatalysis presents an alternative for the CO2
fxation and activation utilizing small organic molecules
that is known as catalysts. Recently, [22–29] N-hetero-
cyclic carbenes (NHCs) [30–32], frustrated Lewis pairs
(FLPs) [33–39], N-heterocyclic bases (NHCBs), [40–43]
polyphenols, [44, 45] quaternary onium hydroxide/quater-
nary [46] onium salts (PTCs), and fuoroalcohols, silanedi-
ols with co-catalysts [47, 48] as well as ionic liquids (ILs)
[49–53] are utilized as catalysts for catalytic CO2 fxation
and activation.
Cl-
O
O
i
S
O
C12H25
O
O
O
O
CO2
R
R
In recent years, the use of surfactant on soft templating
is an efcient way to produce mesoporous silica (dendri-
metic silica fbers morphology (DFNS)). For adsorption
and catalysis approaches as support material, silica having
this morphology are being examined. In order to access
the functional materials more efectively, for reactants, the
outward radial widening of these silicas has higher surface
area. Moreover, DFNS possesses thermally stable, and
intrinsic mesoporous properties and presents high activity.
The DFNS is required to synthesis micro emulsion system,
which has surfactant, water, and oil. Moreover, the particle
size and DFNS morphology may be lightly manipulated
utilizing co‐surfactant and diferent co solvents [54–57].
Ionic liquids (ILs) is introduced as proper homogeneous
catalysts [58] due to their outstanding physicochemical
properties such as negligible wide liquid range, vapour
pressure, excellent solubility, and high ionic conductiv-
ity [59]. Although ILs have many advantages but, in its
recovery, their practical usages are restricted utilizing
some difculties that cause environmental and economic
issues (i.e., pending catalytic reactions, their high viscos-
ity not just limits their mass transfer but also causes their
handling hard). In addition, the utilize of relatively large
values of ILs can cause toxicological issues and is costly.
To produce heterogeneous catalysts, these issues may be
overcome by utilizing immobilization of ILs on solid sup-
ports [60–62].
Scheme 1 Bifunctional phase-transfer catalysts for CO2 fxation
2 Experimental
2.1 General Procedure for the Preparation of IL
6 mmol of imidazole, 6 mmol of potassium hydroxide and
2 ml of dimethylesulfoxide were introduced into a 10 ml
fask and were mixed by stirrer at room temperature for
2 h. Then, 5 mmol of dodecylboromide were added drop
wise to the reaction mixture in 30 min. The mixture was
stirred for another 4 h. Afterwards, 30 ml of water was
added to the reaction mixture and then the fask contents
were introduced into a separating funnel. The mixture was
extracted with 30 ml batches of chloroform for fve times.
Then, the chloroform extracts were combined and washed
with 30 ml batches of water for fve times to remove unre-
acted imidazole. The chloroform extract was dried with
excess of MgSO4. 1mmole of 2,2,-bis (bromomethyl)
propane-1,3-diamine and 2.5 mmol of dodecyl imidazole
were weighed and introduced into a 25 mL fask and sub-
sequently the mixture was placed in a 150 °C oil bath.
After 8 h, the reaction a dark brown gelatinous substance
was obtained. For purifcation, the product was washed
two times with acetone and three times with acetonitrile.
The aim of this study is production of new imidazolium
based ILs to be utilized as nanocatalyst in the CO2 fxa-
tion with epoxides in order to provide cyclic carbonates in
good to excellent yields in very moderate conditions. Imi-
dazolium based ionic liquids are produced. To give IL, the
synthesis approach is according to attach dodecyl bromide
to imidazole ring to obtain dodecyl imidazole and pair-
ing two dodecyl imidazoles by utilizing 1,3-Diamino-2,2-
bis(bromomethyl)propane, subsequently. This IL attaching
by etherifcation on DFNS nanoparticle surfaces (Scheme 1).
2.2 General Procedure for the Preparation of FPS
Tetraethyl orthosilicate (2.08 g) and tripolyphosphate
(3.67 g) were dissolved in a solution of cyclohexane
(30 mL) and 1-pentanol (1.5 mL). A stirred solution of
CPB (1 g) and urea (0.5 g) in water (30 mL) was then
added to the top mixture. The resulting mixture was
1 3

Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation of Carbon Dioxide with Epoxides…
continually stirred for 45 min at room temperature and
then placed in a tefon-sealed hydrothermal reactor and
heated at 120 °C for 5 h. The FPS was then isolated by
centrifugation, washed with deionized water and acetone,
and dried in a drying oven.
The reactor vessel was placed under a constant pressure of
carbon dioxide and then heated to 70 °C for 2 h. Then the
reactor was cooled to ambient temperature, and the result-
ing mixture was transferred to a 50 mL round bottom fask.
Upon completion, the progress of the reaction was moni-
tored by TLC when the reaction was completed, EtOH was
added to the reaction mixture and the KCC-1/IL/HPW NPs
was separated by flteration. Then the solvent was removed
from solution under reduced pressure and the resulting prod-
uct purifed by recrystallization using n-hexane/ethyl acetate.
2.3 Total Approach for the Synthesis
of DFNS/3‑Chloromopropyl MNPs
A mixture was prepared by mixing 200 mg of FeNi3/DFNS
in 20 ml of THF followed by the addition of 20 mmol of
NaH via ultrasonication. After that, 22 mmol of 3-chlo-
romopropyl trimethoxysilane were added into the mixture at
room temperature and stirred for 16 h at 50 °C. The resultant
mixture was fltered and washed with ethanol and deionized
water. The fltered solids were then dried in vacuum condi-
tion at 50 °C for 3 h.
3 Results and Discussion
In this study, solution of DFNS is synthesized with taking
into account of reported approaches and after that became
suitable utilizing (3-Cloropropyl)trimethoxysilane, followed
by reductive amination for making the related co-immobi-
lized IL. Scheme 2 shows this process.
2.4 Total Approach for the Synthesis of IL/DFNS NPs
The morphology of the produced nanoparticles of
DFNS and IL/DFNS were evaluated by TEM and FE-SEM.
Figure 1a demonstrated that there are silica fbers and layer
of nonporous silica. Figure 1a and b shows TEM and FE-
SEM images. As can be observed, the DFNS samples
possess a wrinkled radial structure and additionally solid
spheres with 400 nm diameter. Wrinkled fbers (7 nm) can
be observed by close study of these images. These fbers
commonly grown from the center of spheres and radially
adjusted. Moreover, the wrinkled radial structure overlap
makes the conical pores and this hierarchical open channel
structure along with fbers may lead to transfer the mass
of reactants for performing easier. In addition, it can rise
access to active sites. As can be seen in Fig. 1b and d,
DFNS/3-chloromopropyl (200 mg) are difused in a solu-
tion (80 mL) of ethanol, deioned water (20 mL) and 28 wt%
concentrated ammonia aqueous solution (NH3·H2O, 2.0 mL)
and fnally by adding 20 mg of IL. The produced suspension
has been washed, repeatedly, after intense stirring fltered
frequently and then dried under the temperature of 50 °C
at air presence.
2.5 General Procedures for Preparation of Cyclic
Carbonate
IL/DFNS NPs (5 mg) and epoxide derivatives (1 mmol) were
charged into the reactor vessel without using any co-solvent.
NH2 NH2
NH2 NH2
Br-
N
Br-
N
Br Br
Br
N
NH
C12H25
N
C12H25
N
N
C12H25
N
O
O
S
C12H25
N
O
S
O
O
i
Cl-
O
i
EtO
EtO Si
EtO
Cl
Cl
Cl
N
N
HN
HN
N
O
i
Cl-
S
O
O
i
S
O
C12H25
O
O
DFNS
Scheme 2 Schematic illustration of the IL/DFNS NPs preparation
1 3

P. Zhang, R. Zhiani
Fig. 1 TEM images of DFNS
MNPs (a); IL/DFNS NPs (b);
FE-SEM images of DFNS NPs
(c); IL/DFNS NPs (d)
Fig. 2 TGA curves of IL/DFNS NPs
Fig. 3 XPS spectra of IL/DFNS NPs
after modifcation, the morphology of DFNS did not vary
from FE-SEM and TEM images of IL/DFNS NPs. TGA
analysis of IL/DFNS NPs is proved in Fig. 2. The sol-
vent deletion of physisorbed and chemisorbed on the IL/
DFNS material surface causing the weight loss. Moreover,
the weight loss in the temperature between 250–450 °C
is near 28.1 wt%, which is related to the organic group
derivatives. Factually, due to exiting the DFNS NPs, the
residual mass after the decomposition of nanoparticles of
IL/DFNS.
In this work, we use XPS for studying the chemical sec-
tions on the IL/DFNS NPs level. For the as gathered catalyst,
1 3

Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation of Carbon Dioxide with Epoxides…
Table 1 Structural parameters of DFNS, and the IL/DFNS NPs
Catalysts
SBET (m2 g−1
)
Va (cm3 g−1
)
DBJH (nm)
DFNS
IL/DFNS
671
348
3.2
1.4
9
5
Table 2 Synthesis of cyclic carbonate by IL/DFNS NPs in diferent
solvents
Entry
Solvent
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
H2O
MeOH
EtOH
i-PrOH
Dioxane
n-Hexane
CHCl3
CH2Cl2
DMF
THF
DMSO
CH3CN
EtOAc
Toluene
Anisole
Solvent-free
Solvent-free
Solvent-free
Solvent-free
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
3
2
1
–
–
–
–
–
–
31
33
19
28
27
22
38
48
49
98
98
98
71
Fig. 4 EDX spectra of IL/DFNS NPs
9
10
11
12
13
14
15
16
17
18
19
Reaction conditions: propylene oxide (1 mmol), IL/DFNS NPs
(10 mg), and CO2 1.5 MPa, at 120 °C
aIsolated yields
Fig. 5 Three-dimensional of AFM images of IL/DFNS NPs
Fig. 3 demonstrates a scheme of XPS. Peaks of C, O, Cl, and
N are shown and the existence of N1s additional confrmed
that DFNS are functionalized using the imidazolium. More-
over, the attendance of ions of Cl− (the imidazolium counter
ion) was specifed by a sharp peak (in 287 eV). This dem-
onstrates that there is imidazolium moiety into the catalyst.
Figure 4 shows the origins in the catalyst that determined by
EDX analysis. Figure 4 indicates the pattern of EDX showed
whole the elements, which stand in IL/DFNS NPs like nitro-
gen, silicon, carbon, oxygen, and chlorine. These NPs level
roughness is specifed by AFM (atomic force microscopy)
analysis. Figure 5 shows topographic scheme and the more
height region demonstrated by the brighter yellowish white
color enhanced by decreasing T/W, suggesting the increased
in the level roughness of catalyst.
diameter and the specifc surface area as well as the total
pore volume values are shown in Table 1. The BET results
demonstrated that the active surface area of the IL/DFNS
and DFNS are equal to 348 and 671 m2 g−1, respectively.
The results of our experiments showed that the specifc sur-
face area decreased after melamine intercalation. In addition,
the pore volume and average pore radius increased using
melamine. It was determined that melamine intercalation
has a more porous network structure.
In this apparatus, the conditions of reaction are optimized
by propylene oxide and carbon dioxide for the production of
cyclic carbonates catalyzed by nanoparticles of IL/DFNS.
The infuences of various parameters like time and solvent
on the model reaction are presented in Table 2. Various
solvents are utilized to study their efect on the synthesis
of cyclic carbonates. Our outcomes indicated that no prod-
uct is produced by polar protic solvents like isopropanol,
methanol, ethanol, and water. Polar protic solvents like
N2 adsorption–desorption isotherm analysis is done to
analyze the specifc surface area and porosity of the prod-
ucts. In accordance to the BJH method, the mean pore
1 3

P. Zhang, R. Zhiani
100
90
80
70
60
50
40
30
20
10
0
EtOAc, DMF, and DMSO demonstrated that moderate per-
formance in cross-coupling yields. In the present study, the
outcomes indicated that solvents are less efcient compared
to common heating under solvent-free conditions. The cross-
coupling reaction efciency in the case of carbonylation is
higher in less polar solvents like toluene and/or anisole. The
reaction is done under optimum conditions in the attend-
ance of IL/DFNS NPs (10 mg) and the progress of reaction
is analyzed by utilizing GC to study the reaction time. We
found that proper product yields are archived after 120 min.
The infuences of various factors for the model reaction
are studied by IL/DFNS nanoparticles. As can be observed
in Fig. 6, like other factors, the catalyst value is impressive
in yields. In addition, low the product yields of the cycload-
dition reaction are achieved in the lack of the catalyst. The
cyclic carbonate products demonstrated moderate yields
using weighted quantities of IL/DFNS NPs (1–4 mg). The
optimum value of IL/DFNS NPs for the model reaction is
determined to be 5 mg.
30
40
50
60
70
80
90
Temperature (oC)
Fig. 7 Efect of temperature on yield of cyclic carbonate
As seen in Table 3, various epoxides are studied in the
case of the investigation of the substrate scopes in this novel
one-pot approach for the production of cyclic carbonates.
Table 3 shows that, for all substrate, the catalyst is active.
It is determined that glycidyl ethers (entry 4–12) are con-
verted to their relating cyclic carbonates in high to excel-
lent products, nevertheless, styrene oxides (entry 13–18)
prepared carbonates in moderate products. The correspond-
ing cyclic carbonates 2j as well as 2 k are achieved in good
yields and moderate enantioselectivities while enantiopure
styrene oxides 19 and 20 are utilized as substrates (78.3%
and 66.7%), and the stereochemistry inversion of the cyclic
carbonates may be due to the electron-withdrawing nature of
the benzene ring that causes a nucleophilic ring opening of
styrene oxide at the methylene bond and the methine bond.
We compared the catalytic performance of our catalyst
with literature reported catalysts for the synthesis of cyclic
carbonate. Table 4 clearly demonstrates that lower tempera-
ture, the minimum amount of catalyst, lower pressure of
carbon dioxide and shorter reaction time were required for
CO2 transformation, using IL/DFNS NPs, while an appropri-
ate, highly perfect, performance of the present catalyst was
observed for the this reaction.
The efect of temperature on the reaction is shown in
Fig. 7. As observed, cyclic carbonate production enhanced to
around 98% at the temperature of 70 °C under 1.0 MPa CO2
pressure after 120 min. Nevertheless, because of a negligi-
ble value of specifc by products like olefn isomerization, a
further enhance in temperature caused in a slight reduce in
the amount of the product. Thus, for the parallel reactions of
CO2 and epoxide, the optimum temperature is around 70 °C.
The pressure of CO2 had a considerable infuence on the
parallel reaction. As observed in Fig. 8, the rate of reaction
enhanced under pressures in the range of 0.8 and 1.0 Mpa,
rapidly. Based on previous works, we have concluded that
enhancing the reaction pressure is desirable for cyclic car-
bonate synthesis until the pressure is below 1.0 MPa. Thus,
the CO2 pressure of 1.0 MPa is recognized as a particular
condition. Initially, the following conditions are considered
for the reaction: (the temperature of 70 °C at 4 h (10 mol%)).
Various oxidants are utilized for enhancing yields of prod-
uct. The reaction product is highly sensitive to the base.
The mechanism of the bifunctional phase-transfer IL/
DFNS NPs according to the experimental facts in the case
100
90
80
70
60
50
40
30
20
10
0
100
90
80
70
60
50
40
30
20
10
0
0
1
2
3
4
5
6
7
Catalyst amount (mg)
0.4
0.6
0.8
1
1.2
1.4
CO2 Pressure (MPa)
Fig. 6 Efect of increasing amount IL/DFNS NPs on yield of cyclic
carbonate
Fig. 8 Efect of CO2 pressure on the synthesis of cyclic carbonate
1 3

Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation of Carbon Dioxide with Epoxides…
Table 3 Synthesis of cyclic
Entry
1
Epoxides
Product
Yield
(%)b
98
carbonate derivatives catalyzed
by IL/DFNS NPs
O
O
Me
O
O
O
O
Me
2
3
4
O
91
92
86
O
O
Et
O
O
Et
O
Bun
Bun
O
O
Octn
O
O
Octn
O
5
6
7
8
O
94
98
96
98
HO
PhO
Cl
O
O
HO
O
O
O
O
PhO
Cl
O
O
O
O
O
O
BnO
O
O
BnO
1 3

P. Zhang, R. Zhiani
Table 3 (continued)
O
9
O
O
O
95
BzO
O
O
O
BzO
OMe
96
93
82
78
75
O
O
O
O
10
OMe
O
O
O
O
Me
O
11
12
13
14
Me
O
O
O
O
O
O
O
O
O
O
O
O
O
O
F
F
O
O
79
15
O
O
Cl
Cl
1 3

Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation of Carbon Dioxide with Epoxides…
Table 3 (continued)
O
O
O
77
83
85
16
O
O
O
O
Br
Br
O
17
Me
Me
O
O
18
O
O
MeS
MeS
O
O
O
80
19
78 ee
O
O
O
O
O
81
20
75 ee
aReaction condition: epoxide derivatives (1 mmol), IL/DFNS NPs (5 mg), CO2 1 Mpa (balloon), 2 h
bYield refers to isolated product
of the fxation of carbon dioxide with epoxides was sug-
In the last step, we have done a leaching study to assay
whether this catalytic approach is really heterogeneous or
attended catalysis is increased homogeneously using some of
IL materials leaching into the solution. Firstly, the reaction is
conducted utilizing optimized conditions, in the attendance
of a ten-runs reused batch of the catalyst. After a few minute,
catalyst is taked by hot fltration and the remaining solution
is stirred. Figure 9 indicates the CO2 fxation vs time by
a ten-runs reused catalyst batch (signed as a green curve),
gested in Scheme 3. Firstly, epoxide was activated using
IL/DFNS via hydrogen-bonding interaction among atoms
of O and N–H for forming intermediate A that endures a
nucleophilic attack of Cl− to provide intermediate B that
then attacks carbon dioxide to get intermediate C, and after
that the intramolecular ring-closing of intermediate C pre-
pares cyclic carbonate with a IL/DFNS release to create
the carbonate ready to the next catalytic cycle.
1 3

P. Zhang, R. Zhiani
Table 4 Comparison of the
catalytic efciency of IL/DFNS
NPs with various catalysts for
synthesis of cyclic carbonate
Entry Catalyst
MPa (CO2) Solvent Tempera- Amount catalyst Time (h) Yield (%)
ture (°C)
1
2
NaBr
KBr
2
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
–
125
125
125
125
125
125
125
125
125
110
120
90
1 mmol
1 mmol
1
1
1
1
1
1
1
1
1
6
3
6
30 [63]
52 [63]
68 [63]
86 [63]
46 [63]
88 [63]
87 [63]
42 [63]
90 [63]
91.7 [64]
89 [65]
99 [66]
2
2
3
4
5
6
KI
1 mmol
Bu4NBr
Bu4NCl
Bu4NI
2
2
1 mmol
1 mmol
2
2
1 mmol
1 mmol
7
8
9
10
11
12
[bmim]Br
[bmim]Cl
[bmim]I
BImBr_SiO2
GO-DMEDA-I
Organic–inor-
ganic hybrid
catalyst
2
2
1 mmol
1 mmol
3.55
2
1
1 mol (%)
0.65 mol (%)
1 mol (%)
–
–
13
14
15
16
17
18
19
20
21
22
23
24
Mim
HBimBr
HMimBr
HEimBr
HMimCl
HPyBr
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1
1
1
1
1
–
–
–
–
–
–
–
–
–
–
–
–
120
120
120
120
120
120
120
110
100
100
100
70
1 mol (%)
1 mol (%)
0.5 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
0.5 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
0.5 mol (%)
2
2
2
2
2
2
2
3
24
24
24
2
– [67]
77.7 [67]
59.8 [67]
85.8 [67]
47.4 [67]
31.6 [67]
34.9 [67]
99 [68]
63 [69]
61 [69]
58 [69]
98
HTeaBr
FDU-HEIMBr
Et4N+Cl–
n-Bu4N+Cl–
n-Bu3MeN+Cl–
IL/DFNS
Reaction conditions: epoxide (1 mmol), and CO2 in diferent solvents and in diferent amounts of catalyst,
temperature, and time
Cl-
C12H25
N
N
N
N
C12H25
N
N
H
H
O
i
i
S
O
O
S
O
O
O
O
Cl-
C12H25
Cl-
C12H25
O
C
O
Cl
R
N
N
N
N
N
N
N
N
C12H25
C12H25
Intermediate B
N
N
N
N
H
H
H
H
i
i
i
i
O
O
OS
O
OS
O
O
S
O
S
O
O
O
O
O
O
O
O
O
O
Cl
O
R
Cl-
Intermediate A
R
R
Intermediate C
Scheme 3 Proposed catalytic cycle of the fxation of CO2 by epoxides
1 3

Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation of Carbon Dioxide with Epoxides…
it can be reused for ten-times without considerable loss in
its catalytic activity, a necessary perspective of clean chem-
istry. It can be rapidly recycled utilizing many washings by
ethanol. Then, it is dried at 25 °C and was recycled for many
times with approximately unaltered catalytic activity (refer
to Fig. 11).
Finally, we have investigated after the passage of the
10th catalytic fxation of carbon dioxide at the specifed
premium conditions with some assay for ensuring whether
the recovered catalyst structure was maintained or not (refer
to Fig. 12). As can be seen in Fig. 12a XPS, pattern of the
reproduced catalyst demonstrated that the structure of cata-
lyst remained completely intact in recycling. In addition,
the loading values of the organic materials in the nanoparti-
cles of IL/DFNS are found after ten reuses using TGA. Fig-
ure 12b shows that their values are identical to the fresh nano
composites. It should be noted that the nano catalyst has
not detected any morphological variations, which is demon-
strated using the FE-SEM schemes that obtained from the
recovered catalyst as seen in Fig. 12c. As seen in Fig. 12d,
the TEM scheme shown that the a generic gray and white
layers placed on the direct chain of IL are IL/DFNS after
the 10 th run.
Fig. 9 Leaching test for catalyst fxation of CO2
and how no addition reagent utilize was identifed when the
catalyst was removed from the combination (signed as a red
curve).
We have explored the scope for scale-up of organic chem-
istry using a large batch. We performed the reaction on fve
scales; 1 mol, 1.5 mol, 3 mol, 3.5 mol, and 5 mol, in each
case running the reaction. It proved to be very scalable,
afording isolated yields of 94%, 96%, 98%, 98%, and 97%,
respectively, at the fve reaction scales (Fig. 10). This unit
should prove an efective tool for the development of scale-
up chemistry.
4 Conclusions
Generally, under moderate conditions, a series of bifunc-
tional IL/DFNS as phase-transfer catalysts for the fxation
of CO2 with epoxides were demonstrated to provide cyclic
carbonates in good to excellent yields. These bifunctional
catalysts were easily prepared and structure-tuneable, as well
as prove high efciency for the CO2 fxation under ambi-
ent pressure. In addition, this catalyst are produced for the
kinetic resolution of rac-epoxides using CO2 for producing
chiral cyclic carbonates.
The catalyst reusability of the IL/DFNS nanoparticles
was additionally investigated. It was found that it can be
reused up to ten times without high loss in its catalytic activ-
ity, an outlook necessary perspective of clean chemistry. The
catalyst reusability of the IL/DFNS NPs up to successive
ten-times, was additionally investigated for catalyst fxation
of CO2 under optimized conditions. It was demonstrated that
100
90
80
70
60
50
40
30
20
10
0
1
2
3
4
5
6
7
8
9
10
Reuse
Fig. 11 The reusability of catalysts for catalyst fxation of CO2
Fig. 10 Reactions performed in the scale-up
1 3

P. Zhang, R. Zhiani
Fig. 12 a XPS, b TGA, c FE-SEM, and d TEM images of the recovered IL/DFNS NPs after the 10th run for catalytic fxation of CO2
15. Li PZ, Wang XJ, Liu J, Phang HS, Li Y, Zhao Y (2017) Chem
Mater 29:9256–9261
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