Catalytic synthesis of cyclic carbonates from epoxides and carbon dioxide by magnetic UiO-66 under mild conditions

Article abstract of DOI:10.1002/aoc.3656

The catalytic activity of UiO-66@Fe₃O₄@SiO₂ catalyst was investigated in the fixation of carbon dioxide with epoxides under mild conditions. In this manner, a facile magnetization of UiO-66 was achieved simultaneously by s

Full text of DOI:10.1002/aoc.3656

Received: 14 June 2016
DOI 10.1002/aoc.3656
Revised: 30 August 2016
Accepted: 11 September 2016
F U L L PA P E R
Catalytic synthesis of cyclic carbonates from epoxides and carbon
dioxide by magnetic UiO‐66 under mild conditions
Mahbube Delavari | Farnaz Zadehahmadi | Shahram Tangestaninejad | Majid Moghadam |
Valiollah Mirkhani | Iraj Mohammadpoor‐Baltork | Reihaneh Kardanpour
Department of Chemistry, Catalysis Division,
The catalytic activity of UiO‐66@Fe3O4@SiO2 catalyst was investigated in the fix-
University of Isfahan, Isfahan 81746‐73441, Iran
ation of carbon dioxide with epoxides under mild conditions. In this manner, a facile
Correspondence
Shahram Tangestaninejad or Majid Moghadam or
magnetization of UiO‐66 was achieved simultaneously by simply mixing this metal–
organic framework and silica‐coated Fe3O4 nanoparticles in solution under sonica-
tion. The prepared catalyst was characterized using Fourier transform infrared and
Valiollah Mirkhani, Department of Chemistry,
Catalysis Division, University of Isfahan, Isfahan
81746‐73441, Iran.
Email: stanges@sci.ui.ac.ir; moghadamm@sci.ui.
UV–visible spectroscopies, X‐ray diffraction, transmission and field emission scan-
ning electron microscopies, N2 adsorption and inductively coupled plasma atomic
emission spectroscopy. This new heterogeneous catalyst was applied as a highly effi-
cient catalyst in the coupling of carbon dioxide with epoxides at mild temperatures
and pressures. Furthermore, it could be easily recovered with the assistance of an
external magnetic field and reused three consecutive times without significant loss
of activity and mass.
ac.ir; mirkhani@sci.ui.ac.ir
KEYWORDS
CO2 fixation, magnetization, metal–organic frameworks, UiO‐66, UiO‐
66@Fe3O4@SiO2
1
|
INTRODUCTION
which limits the wide application of these catalysts. In order
to overcome the separation problem, many heterogeneous
Carbon dioxide, an available, inexpensive, non‐toxic and
renewable carbon resource, has received much attention in
recent decades from both economic and environmental points
of view. Global warming is primarily a problem of accumula-
tion of CO2 as an important greenhouse gas in the atmo-
sphere. So its capture, storage and utilization have received
much attention.[1,2]
One of the most promising methodologies in this area for
chemical fixation of CO2 is its conversion to cyclic carbon-
ates via the reaction of it with epoxides. Cyclic carbonates
have been widely used as synthetic intermediates, aprotic
polar solvents and in many biomedical applications.[3,4]
In recent decades numerous catalytic systems including
metal oxides, ionic liquids, alkali metal salts, Lewis acids,
transition metal complexes, porphyrins, polyoxometalates
and Schiff bases have been developed for this transforma-
tion.[5–14] Generally, these homogeneous catalysts provide
high turnover number and high activity but they often suffer
from difficulty of recycling and separation from products,
catalysts have been developed.
Metal–organic frameworks (MOFs), which are metal–oxo
clusters linked by tunable organic linkers,[15–17] have
attracted increasing attention because of their porosity, tun-
able cavities, various topologies and extraordinary surface
areas, as well as their numerous potential applications in
gas sorption or storage,[18] luminescence,[19] drug release,[20]
optoelectronics,[21] chemical sensing[22] and catalysis.[23–29]
One of the most stable MOF structures, which has been
synthesized by Lillerud and co‐workers, is UiO‐66.[30] This
MOF, which also has high surface area and nanometre pore
size useful for catalysis, has been directly synthesized by
the reaction of the corresponding metals with
benzenedicarboxylate via
method.
a conventional solvothermal
Magnetic nanoparticles such as Fe3O4 nanoparticles
have been widely used in the collection and separation of
bioactive molecules, biomedical applications and targeted
drug delivery. Combination of MOFs and magnetic
Appl Organometal Chem 2016; 1–7
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
1

2
DELAVARI ET AL.
nanoparticles has obvious advantages in adsorption and sep-
aration.[31–34] The separation of magnetic nanoparticles
using a magnet is typically more effective than filtration or
centrifugation and which prevents the loss of catalyst. This
separation is economical, simple and promising for indus-
trial applications.[35] Zhao et al. reported an efficient strat-
egy for fabricating a magnetic MOF as sorbent for
removing organic compounds from simulated water sam-
ples.[31] Yuan and co‐workers reported a facile and environ-
mentally friendly fabrication of a novel type of magnetic
porous MOF‐based nanocomposites that can be potentially
used for targeted drug delivery.[36]
In the work reported in this paper, we successfully syn-
thesized magnetic UiO‐66 as a new hybrid catalyst. The cat-
alytic activity of this new heterogeneous catalyst was
investigated in the chemical fixation of CO2 with epoxides
in the presence of LiBr as co‐catalyst at ambient pressure
and temperature (Scheme 1). This catalyst was highly effi-
cient, stable and reusable in the conversion of epoxides with
CO2 into cyclic carbonates.
2.2 | Magnetization of UiO‐66
In a typical and very simple procedure, Fe3O4@SiO2
(100 mg) and UiO‐66 (60 mg) in methanol were placed in a
25 ml glass vial under ultrasonication for 2 h for the magne-
tization of UiO‐66 in the form of UiO‐66@Fe3O4@SiO2
microspheres. Then, an external magnet was attached to the
outside bottom of the vial, so that the prepared catalyst was
gathered to the bottom of the vial, and the supernatant
discarded, and dried in an air oven at 75 °C.
2.2.1
| General procedure for CO2 fixation
First, the reaction parameters including the type of solvent,
amount of catalyst, the kind and amount of co‐catalyst and
temperature were optimized in the reaction of CO2 with
1,2‐epoxyoctane. Under the optimized reaction conditions,
the reaction of various epoxides (linear and cyclic) with
CO2 was investigated in the presence of UiO‐
66@Fe3O4@SiO2. To a solution of epoxide (1 mmol) in
dimethylformamide (DMF; 3 ml) were added lithium bro-
mide (2 mmol) and the catalyst UiO‐66@Fe3O4@SiO2
(40 mg, 0.023 mmol). Carbon dioxide gas was bubbled into
the solution at atmospheric pressure. The progress of the
reaction was monitored by GC. At the end of each reaction,
the catalyst was separated from the reaction mixture using
an external magnet, washed with DMF and diethyl ether,
and reused. The catalyst was consecutively reused several
times without detectable catalyst leaching or significant loss
of its activity. The amount of Zr and Fe leached in the filtrates
was determined by ICP analysis. The stability of UiO‐
66@Fe3O4@SiO2 was investigated using XRD and FT‐IR
spectroscopy.
2
| EXPERIMENTAL
2.1 | Reagents and methods
All materials were of commercial reagent grade and were
obtained from Merck or Fluka. Fourier transform infrared
(FT‐IR) spectra were obtained with potassium bromide pel-
lets in the range 400–3500 cm−1 with a JASCO 6300 spectro-
photometer. Field emission scanning electron microscopy
(FE‐SEM) was conducted with a Hitachi S‐4700 instrument.
X‐ray diffraction (XRD) patterns were recorded using a
Bruker D8 Advance X‐ray diffractometer equipped with
nickel monochromatized Cu Kα radiation (λ = 1.5406 Ǻ).
Specific surface area was measured by adsorption–desorption
of N2 gas using an Micromeritics ASAP 2000 instrument.
Inductively coupled plasma (ICP) analyses were carried out
with a PerkinElmer Optima 7300 DV spectrometer. GC
experiments were performed with a Shimadzu GC‐16 A
instrument using a 2 m column packed with silicon DC‐200
or Carbowax 20 M. In the GC experiments, n‐decane was
used as the internal standard. An alternating gradient force
magnetometer (AGFM model, Kavir) was used. UiO‐66
was prepared based on the procedure reported by Lillerud
and co‐workers.[30] The Fe3O4 magnetic nanoparticles
(MNPs) were synthesized and coated with silica as reported
in the literature.[37]
3
| RESULTS AND DISCUSSION
3.1 | Characterization of catalyst
The crystallinity of the framework and nanoparticles was
studied using XRD analysis. The XRD pattern of UiO‐66
(Figure 1A) is the same as the profile of UiO‐66 synthesized
previously by Lillerud et al.[30] Also, the XRD pattern of
Fe3O4@SiO2 (Figure 1B) is the same as that of Fe3O4@SiO2
in the literature.[37,38] As can be seen in Figure 1(C), the crys-
tallinity of UiO‐66 and Fe3O4@SiO2 is well retained after the
magnetization reaction, because all diffraction peaks of the
MOF and MNPs can be readily indexed to the pattern of
UiO‐66@Fe3O4@SiO2. Thus the XRD pattern of the new
nanocatalyst indicates that the basic lattice structure of
UiO‐66 is well retained. Also, the sharp peaks indicate the
excellent crystallinity of the framework.
The FT‐IR reflectance spectra of the samples are shown
in Figure 2. The FT‐IR spectrum of UiO‐66 synthesized
according to the literature is shown in Figure 2(A). The peak
at 1550–1630 cm−1 corresponds to C═O of carboxylates
coordinated with the metal centres by oxygen during the
SCHEME 1 Chemical fixation of CO2 with epoxides catalysed by UiO‐
66@Fe3O4@SiO2

DELAVARI ET AL.
3
FIGURE
1
XRD patterns: (A) UiO‐66; (B) Fe3O4@SiO2; (C) UiO‐
66@Fe3O4@SiO2; (D) recovered catalyst
FIGURE 4 SEM–EDX spectrum of UiO‐66@Fe3O4@SiO2 (Al is from the
sample holder)
To investigate the surface morphology of the MOF and
synthesized magnetic MOF, the samples were characterized
using FE‐SEM (Figure 3). FE‐SEM images show a small
cubic inter‐grown architecture for UiO‐66 (Figure 3A), and,
as can be seen in Figure 3(B), the MNPs are homogeneously
dispersed on the surface of UiO‐66. The energy‐dispersive
X‐ray (EDX) results, obtained from FE‐SEM analysis, for
UiO‐66@Fe3O4@SiO2 (Figure 4) clearly show the presence
of C, O, Si, Zr and Fe in the nanocatalyst.
The porous structure of UiO‐66 and the magnetic MOF
were investigated using nitrogen physisorption measurements
(Figure 5), and the textural parameters are presented in
Table 1. The results clearly show a predictable decrease in
pore volume (from 0.558 to 0.411 cm3 g−1) and in the BET
surface area (from 1315 to 532 m2 g−1) which can be attrib-
uted to the blocking of UiO‐66 cavities by surface‐located
iron MNPs due to the magnetization reaction.
FIGURE
2
FT‐IR spectra: (A) UiO‐66; (B) Fe3O4@SiO2; (C) UiO‐
66@Fe3O4@SiO2; (D) recovered catalyst
deprotonation process.[27,28] In each spectrum a weak peak in
the region 1450–1580 cm−1 belongs to C─C in the aromatic
compound of the organic linker. The strong peak at around
1400 cm−1 is ascribed to C─O bond of C─OH group of car-
boxylic acid.
Figure 2(B) shows the FT‐IR spectrum of the synthesized
MNPs which exhibits characteristic bands at 580 cm−1
(Fe─O), 950 cm−1 (Si─OH) and 1091 cm−1
(Si─O─Si),[37,38] which are seen in the spectrum of UiO‐66
after the magnetization reaction (Figure 2C), proving the suc-
cessful synthesis of UiO‐66@Fe3O4@SiO2.
The magnetic properties of the samples are shown in
Figure 6. The magnetic saturation (MS) values of Fe3O4,
Fe3O4@SiO2 and UiO‐66@Fe3O4@SiO2 are about 69.4,
39.4 and 8.1 emu g−1, respectively. The results indicate that
magnetic property of Fe3O4 decreases as a result of silica
coverage and magnetization of UiO‐66, but the saturation
FIGURE 5 N2 adsorption–desorption isotherms: (A) UiO‐66; (B) UiO‐
66@Fe3O4@SiO2 (○, adsorption; •, desorption)
FIGURE 3 FE‐SEM images: (A) UiO‐66; (B) UiO‐66@Fe3O4@SiO2

4
DELAVARI ET AL.
TABLE 1 Textural parameters of UiO‐66 and the prepared catalyst
TABLE 2 Effect of catalyst amount on formation of 1‐octene carbonate
from reaction of 1,2‐epoxyoctane with CO2
a
Pore volume
(cm3 g−1
Specific surface
area (m2 g−1
)
Entry
Amount of catalyst (mg)
Yield after 10 h (%)b
Sample
)
UiO‐66(Zr)
0.558
0.411
1315
1
2
3
4
5
6
Without catalyst
0
30
87
98
98
98
UiO‐66@Fe3O4@SiO2
532.3
Fe3O4@SiO2
30
40
50
60
magnetization value of 8.1 emu g−1 for UiO‐
66@Fe3O4@SiO2 is enough to make it susceptible to a mag-
netic field and easy to isolate from reaction media.
aReaction conditions: 1,2‐epoxyoctane (1 mmol), LiBr (0.2 mmol), DMF (3 ml),
CO2 atmospheric pressure, T = 80 °C.
bGC yield based on starting epoxide.
3.2 | Catalytic experiments
The catalytic activity of UiO‐66@Fe3O4@SiO2 was evalu-
ated in the coupling reaction of epoxides and CO2 to generate
relevant cyclic carbonates. All effective parameters such as
solvent, amount of catalyst, kind of co‐catalyst and tempera-
ture were optimized. At first, the effect of catalyst amount
on the formation of 1‐octene carbonate was investigated
using various amounts of UiO‐66@Fe3O4@SiO2 in the pres-
ence of 1,2‐epoxyoctane with CO2 under atmospheric pres-
sure at 80 °C. The best results are obtained using 40 mg
(0.023 mmol) of UiO‐66@Fe3O4@SiO2. As evident from
Table 2, no product is obtained in the absence of the catalyst.
Also the selectivity for all reactions is almost 100% and no
by‐product is detected by GC analysis.
The effect of solvent was also investigated in the model
reaction. The results, which are summarized in Table 3, show
that the solvent is an important factor in these reactions. In
methanol, only trace amounts of the corresponding carbonate
are obtained in the presence of the catalyst, while in DMF the
yield increases moderately. The positive effect of the solvent
reported by Aresta et al.[39] can be attributed to an increase of
the nucleophilicity of the oxygen atom of the epoxide or CO2
in DMF.
TABLE 3 Effect of solvent on formation of 1‐octene carbonate from reac-
tion of 1,2‐epoxyoctane with CO2
a
Entry
Solvent
Yield after 10 h (%)b
T (°C)
1
2
3
4
5
Dimethylformamide
Dichloromethane
Acetonitrile
98
55
60
8
80
30
50
45
60
Methanol
Tetrahydrofuran
51
aReaction conditions: 1,2‐epoxyoctane (1 mmol), LiBr (0.2 mmol), solvent (3 ml),
CO2 atmospheric pressure, UiO‐66@Fe3O4@SiO2 (0.023 mmol).
bGC yield based on starting epoxide.
TABLE 4 Effect of temperature on formation of 1‐octene carbonate from
a
reaction of 1,2‐epoxyoctane with CO2
Entry
Temperature (°C)
Yield after 10 h (%)b
1
2
3
4
5
Room temperature
20
45
83
98
98
50
70
80
90
aReaction conditions: 1,2‐epoxyoctane (1 mmol), LiBr (0.2 mmol), UiO‐
66@Fe3O4@SiO2 (0.023 mmol), DMF (3 ml), CO2 atmospheric pressure.
bGC yield based on starting epoxide.
TABLE 5 Effect of co‐catalyst on formation of 1‐octene carbonate from
a
reaction of 1,2‐epoxyoctane and CO2
Entry
Co‐catalyst
Yield after 10 h (%)b
1
2
3
4
5
6
Without co‐catalyst
5
86
73
20
65
98
Tetrabutylphosphonium bromide
Tetrabutylammonium bromide
Sodium chloride
Sodium bromide
Lithium bromide
aReaction conditions: 1,2‐epoxyoctane (1 mmol), co‐catalyst (0.2 mmol), UiO‐
66@Fe3O4@SiO2 (0.023 mmol), DMF(3 ml), CO2atmospheric pressure,
T = 80 °C.
FIGURE
6
Magnetic hysteresis: (A) Fe3O4 microspheres; (B)
Fe3O4@SiO2; (C) UiO‐66@Fe3O4@SiO2
bGC yield based on starting epoxide.

DELAVARI ET AL.
5
TABLE 6 Effect of co‐catalyst amount on formation of 1‐octene carbonate
from 1,2‐epoxyoctane and CO2
(0.023 mmol) after 10 h. Upon increasing the amount of
co‐catalyst, no improvement in yield is observed (Table 6).
It is noteworthy that when LiBr is used as catalyst, no
noticeable product is observed in the reaction mixture.
Under the optimized reaction conditions for the catalyst,
the reaction of various epoxides (linear and cyclic) with
CO2 was investigated. All reactions were carried out under
atmospheric pressure of CO2. The results are summarized
in Table 7. Epoxides bearing aromatic, aliphatic, electron‐
withdrawing and electron‐donating substituents are
converted to their corresponding carbonates with 100%
selectivity. The turnover frequencies (TOFs) for reaction
of linear epoxides are higher than those for cyclic epoxides.
a
Entry
Amount of co‐catalyst (mmol)
Yield after 10 h (%)b
1
2
3
4
5
Without co‐catalyst
5
83
90
98
98
0.05
0.1
0.2
0.3
aReaction conditions: 1,2‐epoxyoctane (1 mmol), LiBr as co‐catalyst, UiO‐
66@Fe3O4@SiO2 (0.023 mmol), DMF (3 ml), CO2 atmospheric pressure,
T = 80 °C.
bGC yield based on starting epoxide.
The reactivity of
a disubstituted epoxide such as
cis‐stilbene oxide was also tested and a yield of 23% of
the corresponding cyclic carbonate is produced. It seems
that the less the steric effect, the shorter the reaction time.
It has been well documented that due to the porosity of
MOFs, these materials can be used for storage of various
gases. Therefore, they can increase the local concentration
of CO2 around active sites of the catalyst which in turn
increases the catalytic activity.
Temperature is another factor that influences the cou-
pling reaction. As evident from Table 4, the highest yield
of 1‐octene carbonate is obtained at 80 °C, and increasing
the temperature to 90 °C does not affect the yield or reaction
time.
The results show that in the absence of catalyst or co‐
catalyst no reaction progress is observed which indicates that
the presence of the catalyst as Lewis acid (electrophile) and
co‐catalyst as Lewis base (nucleophile) is necessary for
obtaining the highest yield.[14,40] Since Zr(IV) is a good
Lewis acid,[41,42] various Lewis bases as co‐catalyst were
checked in the reaction of 1,2‐epoxyoctane with CO2 in the
presence of this catalyst (Table 5). LiBr as a co‐catalyst
shows higher activity than quaternary halide salts (ammo-
nium and phosphonium) in this reaction, probably due to less
of a steric effect.
3.3 | Catalyst reuse and stability
The reusability of a catalyst is an important factor from eco-
nomic and industrial points of view. Therefore, we investi-
gated the recyclability of UiO‐66@Fe3O4@SiO2 in the
multiple sequential coupling reaction of 1,2‐epoxyoctane
with CO2. After using the catalyst for three consecutive runs,
the yield is 80% (Figure 7). Zr and Fe leaching was deter-
mined by analysing collected filtrates using the ICP method.
The results show that after using the catalyst for three
The amount of co‐catalyst was also optimized. The
results show that in the presence of 0.2 mmol of co‐catalyst,
the highest yield is obtained for UiO‐66@Fe3O4@SiO2
a
TABLE 7 Results of coupling of various epoxides and CO2 catalysed by UiO‐66@Fe3O4@SiO2
Entry
R
R′
Yield (%)b
Time (h)
TOF (h−1
)
1
2
3
4
5
6
7
8
9
CH3(CH2)3
CH3(CH2)5
ClCH2
H
98
98
98
98
100
95
98
88
23
5
8.7
4.3
7.2
3.0
4.4
1.72
1.4
3.5
0.5
H
10
6
H
Cyclohexyl
(CH3)2CHOCH2
CH2CHCH2OCH2
C6H5
H
14
10
24
30
11
20
H
H
H
(C6H5)OCH2
C6H5
H
C6H5
aReaction conditions: epoxide (1 mmol), LiBr (0.2 mmol), UiO‐66@Fe3O4@SiO2 (0.023 mmol), DMF (3 ml), CO2 atmospheric pressure, T = 80 °C.
bGC yield.

6
DELAVARI ET AL.
[6] Z. Z. Yang, L. N. He, C. X. Miao, S. Chanfreau, Adv. Synth. Catal. 2010,
352, 2233.
[7] R. L. Paddock, Y. Hiyama, J. M. McKay, S. T. Nguyen, Tetrahedron Lett.
2004, 45, 2023.
[8] V. Caló, A. Nacci, A. Monopoli, A. Fanizzi, Org. Lett. 2002, 4, 2561.
[9] H. Kawanami, A. Sasaki, K. Matsui, Y. Ikushima, Chem. Commun. 2003,
896.
[10] C. Chatterjee, M. H. Chisholm, Inorg. Chem. 2012, 51, 12041.
[11] F. Ahmadi, S. Tangestaninejad, M. Moghadam, V. Mirkhani, I.
Mohammadpoor‐Baltork, A. R. Khosropour, Polyhedron 2010, 32, 68.
[12] M. Aresta, A. Dibenedetto, L. Gianfrate, C. Pastore, J. Mol. Catal. A 2003,
204–205 .245–252
[13] D. Tian, B. Liu, Q. Gan, H. Li, D. J. Darensbourg, ACS Catal. 2012, 2, 2029.
[14] T. Chang, H. Jing, L. Jin, W. Qiu, J. Mol. Catal. A 2007, 264, 241.
FIGURE 7 Recyclability of UiO‐66@Fe3O4@SiO2 in the formation of 1‐
octene carbonate from 1,2‐epoxyoctane with CO2
[15] O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, J. Kim,
Nature 2003, 443, 705.
[16] S. Kitagawa, R. Kitaura, S. Noro, Angew Chem. Int. Ed. 2004, 43, 2334.
[17] G. Férey, Chem. Soc. Rev. 2008, 37, 191.
consecutive times, the amount of Zr leached is about 22%,
but no marked Fe is detected in the filtrates using ICP analy-
sis. This means that the catalyst is stable under the reaction
conditions, and can be recovered and reused. The nature of
the recovered catalyst was investigated using FT‐IR and
XRD analyses. The XRD pattern indicates that the basic lat-
tice structure of UiO‐66@Fe3O4@SiO2 is not altered after
three cycles (Figure 1D). Also, by considering the FT‐IR
spectrum, it is proved that the catalyst has retained its nature
during the reaction (Figure 2D).
[18] U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle‐Arndt, J. Pastré,
J. Mater. Chem. 2006, 16, 626.
[19] P. Horcajada, C. Serre, M. Vallet‐Regı´, M. Sebban, F. Taulelle, G. Férey,
Angew. Chem. Int. Ed. 2006, 45, 5974.
[20] M. D. Allendorf, C. A. Bauer, R. K. Bhakta, R. J. T. Louk, Chem. Soc. Rev.
2009, 38, 1330.
[21] L. Jiang, Z. X. Li, Y. Wang, G. D. Feng, W. X. Zhao, K. Z. Shao, C. Y. Sun,
L. J. Li, Z. M. Su, Inorg. Chem. Commun. 2011, 14, 1077.
[22] G. Lu, J. T. Hupp, J. Am. Chem. Soc. 2010, 132, 7832.
[23] F. Zadehahmadi, F. Ahmadi, S. Tangestaninejad, M. Moghadam, V.
Mirkhani, I. Mohammadpoor‐Baltork, R. Kardanpour, J. Mol. Catal. A
2015, 398, 1.
4
| CONCLUSIONS
[24] M. H. Alkordi, Y. Liu, R. W. Larsen, J. F. Eubank, M. Eddaoudi, J. Am.
Chem. Soc. 2008, 130, 12639.
In summary, we have succeeded in designing a novel catalyst
by facile magnetization of UiO‐66 MOF for the synthesis of
cyclic carbonates from epoxides and CO2. The product
separation and catalyst recycling are possible using an exter-
nal magnet. The prepared catalyst can be recovered and
reused up to three times without significant loss of activity
and mass. High activity, selectivity, easy work‐up and
extremely mild reaction conditions are other advantages of
this new catalyst.
[25] M. H. Sun, S. Z. Huang, L. H. Chen, Y. Li, X. Y. Yang, Z. Y. Yuan, B. L. Su,
Chem. Soc. Rev. 2016, 45, 3479.
[26] F. Zadehahmadi, S. Tangestaninejad, M. Moghadam, V. Mirkhani, I.
Mohammadpoor‐Baltork, A. R. Khosropour, R. Kardanpour, Appl. Catal.
A 2014, 477, 34.
[27] R. Kardanpour, S. Tangestaninejad, V. Mirkhani, M. Moghadam, I.
Mohammadpoor‐Baltork, A. R. Khosropour, F. Zadehahmadi,
J. Organometal. Chem. 2014, 761, 127.
[28] R. Kardanpour, S. Tangestaninejad, V. Mirkhani, M. Moghadam, I.
Mohammadpoor‐Baltork, A. R. Khosropour, F. Zadehahmadi, Appl. Catal.
A 2014, 477, 34.
[29] F. Zadehahmadi, S. Tangestaninejad, M. Moghadam, V. Mirkhani, I.
Mohammadpoor‐Baltork, A. R. Khosropour, R. Kardanpour, Appl.
Organometal. Chem. 2015, 29, 209.
ACKNOWLEDGMENTS
We are grateful to the Iranian National Science Foundation
(INSF) project number 93037921 for financial support of this
work.
[30] J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga, K.
P. Lillerud, J. Am. Chem. Soc. 2008, 130, 13850.
[31] X. Zhao, S. Liu, Z. Tang, H. Niu, Y. Cai, W. Meng, F. Wu, J. P. Giesy, Sci.
Rep. 2015, 5, 11849.
REFERENCES
[32] M. R. Lohe, K. Gedrich, T. Freudenberg, E. Kockrick, T. Dellmann, S.
[1] H. Wu, R. S. Reali, D. A. Smith, M. C. Trachtenberg, J. Li, Chem. – Eur. J.
2010, 16, 13951.
Kaskel, Chem. Commun. 2011, 47, 3075.
[33] F. Ke, Y. P. Yuan, L. G. Qiu, Y. H. Shen, A. J. Xie, J. F. Zhu, X. Y. Tian, L.
D. Zhang, J. Mater. Chem. 2011, 21, 3843.
[2] C. Song, Catal. Today 2006, 115, 2.
[34] K. Aguilar‐Arteaga, J. A. Rodriguez, E. Barrado, Anal. Chim. Acta 2010,
674, 157.
[3] K. Biggadike, R. M. Angell, C. M. Burgess, R. M. Farrell, A. P. Hancock, A.
J. Harker, A. J. Irving, W. R. Irving, C. Ioannou, P. A. Procopiou, R. E.
Shaw, Y. E. Solanke, O. M. P. Singh, M. A. Snowden, R. Stubbs, S. Walton,
H. E. Weston, J. Med. Chem. 2000, 43, 19.
[35] A. H. Latham, M. E. Williams, Acc. Chem. Res. 2008, 41, 411.
[36] F. Ke, Y. P. Yuan, L. G. Qiu, Y. H. Shen, A. J. Xie, J. F. Zhu, X. Y. Tian, L.
D. Zhang, J. Mater. Chem. 2011, 21, 3843.
[4] A. A. G. Shaikh, S. Sivaram, Chem. Rev. 1996, 96, 951.
[5] P. Yan, H. Jing, Adv. Synth. Catal. 2009, 351, 1325.
[37] M. Torki, S. Tangestaninejad, V. Mirkhani, M. Moghadam, I.
Mohammadpoor‐Baltork, Appl. Organometal. Chem. 2014, 28, 304.

DELAVARI ET AL.
7
[38] Z. Zarnegar, J. Safari, J. Nanopart. Res. 2014, 16, 1.
[39] M. Aresta, A. Dibenedetto, L. Gianfrate, C. Pastore, J. Mol. Catal. A 2003,
204–205, 245.
How to cite this article: Delavari, M., Zadehahmadi,
F., Tangestaninejad, S., Moghadam, M., Mirkhani, V.,
Mohammadpoor‐Baltork, I., and Kardanpour, R.
(2016), Catalytic synthesis of cyclic carbonates from
epoxides and carbon dioxide by magnetic UiO‐66
under mild conditions, Appl Organometal Chem, doi:
10.1002/aoc.3656
[40] R. L. Paddock, S. T. Nguyen, J. Am. Chem. Soc. 2001, 123, 11498.
[41] G. V. M. Sharma, C. G. Reddy, P. R. Krishna, J. Org. Chem. 2003, 68, 4574.
[42] K. Nikoofar, Z. Khademi, Res. Chem. Intermed. 2016, 42, 3929.
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