Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the cycloaddition of carbon dioxide to allyl glycidyl ether

Article abstract of DOI:10.1016/j.cattod.2014.05.022

In this study, zeolitic imidazolate framework (ZIF-90) was synthesized from Zn(NO₃)₂·4H₂O and imidazolate-2-carboxyaldehyde (ICA), then it was post-functionalized to form F-ZIF-90 using hydrazine followed by quaternization

Full text of DOI:10.1016/j.cattod.2014.05.022

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Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient
catalyst for the cycloaddition of carbon dioxide to allyl glycidyl ether
Tharun Jose, Yeseul Hwang, Dong-Woo Kim, Moon-Il Kim, Dae-Won Park∗
Division of Chemical and Biomolecular Engineering, Pusan National University, Gumjeong-gu, Busan 609-735, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
In this study, zeolitic imidazolate framework (ZIF-90) was synthesized from Zn(NO3)2·4H2O and
imidazolate-2-carboxyaldehyde (ICA), then it was post-functionalized to form F-ZIF-90 using hydrazine
followed by quaternization. The ZIFs were characterized by elemental analysis (EA), BET, XRD, 13C NMR,
FT-IR, and SEM. The surface area and pore volume of F-ZIF-90 were smaller than those of ZIF-90 due to
functionalization inside the pores. The F-ZIF-90 showed excellent catalytic activity for the synthesis of
the cyclic carbonate from allyl glycidyl ether (AGE) and carbon dioxide. The effects of the reaction param-
eters such as catalyst amount, reaction time, CO2 pressure, and reaction temperature on the reactivity of
F-ZIF-90 were also studied, and reaction mechanism including the role of F-ZIF-90 catalyst was proposed.
The F-ZIF-90 catalyst, however, partially lost its crystalline structure and superior catalytic performance
when it was reused.
Received 16 November 2013
Received in revised form 26 March 2014
Accepted 20 May 2014
Available online xxx
Keywords:
F-ZIF-90
Post-functionalization
Cycloaddition
Carbon dioxide
Epoxide
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
fixation of carbon dioxide under mild conditions remains a
challenge.
Carbon dioxide, although abundant, non-toxic, cheap and non-
flammable, poses challenges in its serving as an attractive C1
feedstock owing to its inertness toward many of the chemicals. By
envisaging an efficient catalyst and reactive substrate, CO2 could
be successfully transformed into useful chemicals [1–5]. The reac-
tions of carbon dioxide with oxiranes leading to the formation of
five-membered cyclic carbonates are well-known examples of the
chemical fixation of carbon dioxide [6–9], since the cyclic carbo-
nates can be used for various purposes, such as for aprotic polar
solvents, electrolytes for batteries, and starting materials for reac-
tive polymer synthesis [6]. Among the various catalysts used for
the synthesis of cyclic carbonates from carbon dioxide and epox-
ides [10–16], however, homogeneous catalyst systems suffer from
problems such as separation of catalysts, low cost effectiveness of
the catalyst synthesis process, and low reusability of the catalyst.
Compared with homogeneous catalysts, heterogeneous catalysts
could be easily separated and reused, but these catalysts have the
following disadvantages: low catalytic activity and/or selectivity,
low stability, and high-pressure requirement. Therefore, the devel-
opment of a highly efficient solid catalyst system for the chemical
Metal–organic frameworks (MOFs) are new emerging porous
materials comprising metal centers connected by various organic
linkers to create porous structures with tunable pore volumes,
surface areas, and chemical properties. Enormous MOF materi-
als have been synthesized and their numbers continue to grow
rapidly, because of their zeolite-like properties, such as high inter-
nal surface area and microporosity, well-ordered porous structures
and high absorption capacity [17–20]. Various applications, includ-
ing gas adsorption [21], molecular separation [22], drug delivery
[23], and catalysis [24,25] have been studied for the porous
MOFs.
Among the reported MOFs, the subfamily of zeolitic imid-
azolate frameworks (ZIFs), which are based on transition metals
(Zn, Co) and imidazolate linkers [26–28], have emerged as can-
didates for the fabrication of molecular sieve membranes and
catalysts owing to their zeolite-like permanent porosity, uni-
form pore size, and exceptional thermal and chemical stability.
Recently, Yaghi et al. [29] reported the new sodalite (SOD) topol-
ogy ZIF-90 through solvothermal reaction of zinc(II) salt and
imidazole-2-carboxyaldehyde (ICA). ZIF-90 is not only highly sta-
ble but also shows permanent microporosity with a narrow size
of the six-membered ring pores [29]. Furthermore, the imidazole
linker in ZIF-90 contains a carbonyl group, which has a favor-
able chemical noncovalent interaction with CO2. In addition, the
∗
Corresponding author. Tel.: +82 51 510 2399; fax: +82 51 512 8563.
E-mail address: dwpark@pusan.ac.kr (D.-W. Park).
http://dx.doi.org/10.1016/j.cattod.2014.05.022
0920-5861/© 2014 Elsevier B.V. All rights reserved.
Please cite this article in press as: T. Jose, et al., Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the
cycloaddition of carbon dioxide to allyl glycidyl ether, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.05.022

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Scheme 1. Post-functionalization of ZIF-90 to produce quaternized F-ZIF-90.
presence of the free aldehyde groups in the framework allows
the covalent functionalization of ZIF-90 with amine group via
an imine condensation reaction [29]. Recently, room-temperature
synthesis [30] and water-based synthesis [31] are reported to
obtain a controllable submicrometer-sized particle. Covalent post-
functionalization technique was applied to prepare molecular sieve
ZIF-90 membranes for enhanced hydrogen separation [32].
In this study, ZIF-90 containing free aldehyde groups in the
framework was prepared and quaternized to produce function-
alized F-ZIF-90, then it was used as an efficient heterogeneous
catalyst for the solventless synthesis of cyclic carbonates from car-
bon dioxide and epoxides. It showed much higher activity than
other heterogeneous catalysts reported by previous literatures.
2.3. Synthesis of cyclic carbonate from AGE and CO2
The synthesis of allyl glycidyl carbonate (AGC or 4-[(prop-
2-en-1-yloxy)methyl]-1,3-dioxolan-2-one) was performed by the
cycloaddition of carbon dioxide to AGE (allyl glycidyl ether
or 2-[(prop-2-en-1-yloxy)methyl] oxirane). The ZIF catalyst was
weighed in air and introduced into a 20-mL reactor containing
40 mmol of AGE under solvent-free conditions, and refluxed in an
autoclave at a desired temperature with stirring under CO2 atmo-
sphere at a pressure of 0.65–1.55 MPa. In a semi-batch operation,
the reactor pressure was maintained constant by a back-pressure
regulator. The reactor was heated to the desired temperature,
and then the reaction was started by stirring the reaction mix-
ture at 600 rpm. After the completion of the reaction time, the
cycloaddition was stopped by cooling the reaction mixture to room
temperature and venting the remaining CO2. The product AGC was
dissolved in dichloromethane and filtered to remove the catalyst.
The conversion of AGE was obtained from gas chromatography (GC,
HP 6890, Agilent Technologies, Santa Clara, CA, USA) data.
2. Experimental
2.1. Preparation of catalyst
The synthesis of ZIF-90 was carried out with a slight modifi-
cation to the synthesis procedure described by Huang et al. [33].
Imidazole-2-carboxyaldehyde (0.029 g) was slowly added to a solu-
tion of zinc nitrate tetrahydrate [Zn(NO3)2·4H2O] (0.054 g) in DMF
(3 mL) under stirring at room temperature for 1 h. Then the mixture
was heated to 100 ◦C for 18 h. The precipitated solid was filtered
and thoroughly washed with ethanol and dried in vacuum oven for
24 h.
The quaternary ammonium group functionalized one (F-ZIF-90)
was prepared via hydrazone containing ZIF as shown in Scheme 1.
Dried ZIF-90 crystal (1.1 mmol, 0.28 g) was reacted with hydrazine
(N2H4, 1 M, 10 mL) in THF at room temperature for 4 h under stirring
followed by washing with THF and dried under vaccum for 24 h
to form hydrazone containing ZIF, then it was mixed with CH3OH
(50 mL) and NaI (0.989 g). After adding CH3I (0.6 mL) drop wisely,
the quaternization was carried out under stirring at 80 ◦C for 20 h
to obtain F-ZIF-90.
3. Results and discussion
3.1. Characterization of the ZIF-90 and F-ZIF-90
To perform the post-synthesis functionalization on crystals of
ZIF-90 its porosity was first examined by BET analysis. The N2
adsorption isotherm shown in Fig. 1 indicates the permanent poros-
ity of the ZIF-90 framework. The small step at higher relative
pressure with a hysteresis loop is attributed to the formation of
mesopores [34]. The presence of imine and quaternary ammonium
functionalities in F-ZIF-90 severely constrict the pore aperture and
700
600
500
2.2. Characterization
FT-IR spectra of ZIF-90 and F-ZIF-90 were obtained using a
Bruker A.M GMBH (960981(A)). The percentage nitrogen in the
ZIFs was determined using a Vario-EL III CHN Elemental Analyzer,
which used combustion in a pure oxygen environment to con-
vert the sample elements to simple gases such as CO2, H2O, and
N2. Wide-angle X-ray diffraction (WXRD) with a Rigaku D/Max
2500 diffractometer using Cu-K␣ radiation (40 kV, 50 mA) was
used to calculate d-spacing of the samples. The scanning electron
microscopy (SEM) micrographs were obtained on a Hitachi S-47000
microscope operated at 30 kV. The textural properties of the sam-
ples were analyzed by recording the N2 adsorption isotherm at
77 K, using a BET apparatus (Microneritics ASAP 2020). Before gas
sorption analysis, ZIFs were pretreated for 12 h at 120 ◦C under vac-
uum. The specific surface area was determined using the BET model
equation. 13C cross-polarization MAS NMR spectra were measured
with a recycle delay of 5 s for a total of 1024 scans with the fol-
lowing conditions: magic-angle spinning at 5 kHz, and a л/2 pulse
of 7 ␮s.
ZIF-90
400
300
F-ZIF-90
200
100
0
0.0
0.2
0.4
0.6
0.8
1.0
P/Po
Fig. 1. Nitrogen isotherms of ZIF-90 and F-ZIF-90 measured at 77 K (O: desorption,
X: adsorption).
Please cite this article in press as: T. Jose, et al., Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the
cycloaddition of carbon dioxide to allyl glycidyl ether, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.05.022

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3
ZIF-90
O
1
2
N
N
2
Zn
Zn
3
3
F-ZIF-90
1678
3
1
1618
1600
ZIF-90
2000
1800
1400
1200
1000
800
600
300
250
200
150
100
50
0
Wavenumber (cm-1)
ppm
Fig. 3. FT-IR spectra of F-ZIF-90 and F-ZIF-90.
(a)
4
N
I
N
1
4
2
4
N
N
Zn
Zn
3
3
3
2
1
4
F-ZIF-90
300
250
200
150
100
50
0
Fig. 4. WXRD patterns of ZIF-90 and F-ZIF-90.
ppm
(b)
F-ZIF-90 due to the functionalization of ZIF-90 with N2H4
(hydrazine) followed by the treating with alkyl halide to form it.
The morphology of F-ZIF-90 is shown in Fig. 5. In the SEM image,
well-defined crystals of about 1–3 ␮m were observed.
Fig. 2. 13C NMR spectra of (a) ZIF-90 and (b) F-ZIF-90.
prevent molecules from accessing the interior of the pores, as con-
firmed by its gas adsorption isotherm behavior. The BET surface
area of 1328 m2/g for ZIF-90 was reduced to be 763 m2/g for F-ZIF-
90.
3.2. Performance of ZIF-90 and F-ZIF-90
The performance of ZIF-90 and F-ZIF-90 for the synthesis of AGC
was tested under batch and constant pressure semi-batch opera-
tion after a reaction time of 6 h at 120 ◦C. The conversion of AGE,
selectivity and yield of AGC are presented in Table 2. Quaternized
catalyst F-ZIF-90 showed much higher AGE conversion and AGC
yield than unfunctionalized ZIF-90. With only 20 mg (0.95 wt%) of
F-ZIF-90 catalyst 96.6% AGC yield was obtained at constant CO2
pressure of 1.17 MPa at 120 ◦C. The nucleophilic nature of the iodide
To ensure aldehyde functionality of ZIF-90, the solid-state 13C
CP MAS NMR spectra were measured and the results are shown
in Fig. 2. The 13C NMR of ZIF-90 showed the resonances at 129,
150, and 178 ppm for the symmetrically equivalent 3-carbon atoms
of the imidazolate, the 2-carbon atom of the imidazolate and the
aldehyde carbon atom, respectively. The FT-IR spectrum of ZIF-90 is
shown in Fig. 3. A strong band at 1678 cm−1 (C O) provided further
evidence for the presence of aldehyde in bulk ZIF-90, and the post-
functionalization was confirmed by its absence in F-ZIF-90.
WXRD results for ZIF-90 and F-ZIF-90 are presented in Fig. 4.
From the figure, even though the F-ZIF-90 maintained the
basic crystalline structure of the parent framework (ZIF-90), its
crystallinity is a little lower compared to ZIF-90 due to the quater-
nization process.
Table 1
Elemental analyses of ZIF-90 and F-ZIF-90.
CHNO from elemental analysis
Catalyst
C (wt%)
H (wt%)
N (wt%)
O (wt%)
ZIF-90
F-ZIF-90
33.86
27.18
2.47
2.90
18.59
21.83
15.32
6.57
Table 1 also shows elemental analysis results of the ZIF-90 and
F-ZIF-90. Results demonstrates the increase of nitrogen amount for
Please cite this article in press as: T. Jose, et al., Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the
cycloaddition of carbon dioxide to allyl glycidyl ether, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.05.022

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100
80
60
40
20
Conversion
Selectivity
Fig. 5. SEM image of F-ZIF-90.
0
0
10
20
30
40
Table 2
Catalyst amount (mg)
The reactivity of ZIF-90 and F-ZIF-90 at batch and semi-batch operations.
Fig. 7. Effect of catalyst amount on the reactivity of F-ZIF-90 under semi-batch
Catalyst
Conv. (%)
Sel. (%)
Yield (%)
operation. (AGE = 18.1 mmol, T = 120 ◦C, PCO = 1.17 MPa, reaction time = 6 h).
2
ZIF-90a
64.8
76.9
86.1
98.7
61.8
94.6
50.4
97.9
40.0
72.7
43.4
96.6
F-ZIF-90a
ZIF-90b
Table 3
F-ZIF-90b
The effects of reaction temperature on the reactivity of F-ZIF-90.
Reaction conditions: AGE = 18.1 mmol, catalyst = 20 mg (0.177 mol%), T = 120 ◦C,
reaction time = 6 h.
Temp. (◦C)
Conv. (%)
Sel. (%)
Yield (%)
60
80
100
120
140
160
4.1
37.1
62.2
98.7
99.4
99.2
85.4
93.1
96.8
97.9
96.2
90.8
3.5
34.5
60.2
96.6
95.6
90.1
a
Batch operation with initial pressure of CO2 = 1.17 MPa.
Semi-batch operation with constant pressure of CO2 = 1.17 MPa.
b
anion of the functional group is known to activate the ring opening
of AGE [2,3,11].
Reaction conditions: AGE = 18.1 mmol, catalyst = 20 mg (0.177 mol%), reaction
time = 6 h, PCO = 1.17 MPa, semi-batch operation.
The reaction time has a prominent influence on the catalytic
activity as revealed in Fig. 6 for the synthesis of AGC at semi-
batch operation. The conversion of AGE in the first hour was 46%
procuring a maximum of >98% in 6 h and thereafter remained
nearly unchanged. The selectivity to AGC was very high and main-
tained throughout whole the reaction time. Thus, 6 h was chosen
as reaction time for the further kinetic studies. In order to check a
2
possible contribution of a homogeneous catalytic action of active
zinc species leached into solution, hot catalyst filtration test was
performed after 3 h of reaction. As shown in Fig. 6, no further AGE
conversion in the filtrate occurred after catalyst removal at the reac-
tion temperature, indicating that catalysis is not due to the soluble
homogeneous species [35].
The effects of catalyst amount on the reactivity of F-ZIF-90
for the cycloaddition of CO2 and AGE were studied under semi-
batch operation at 120 ◦C with CO2 pressure of 1.17 MPa and the
results are shown in Fig. 7. Catalyst amounts varying from 5 to
40 mg which proportionately corresponds to 0.24 wt% (relative to
AGE) to 1.9 wt% were investigated. The catalytic activity was found
to be increasing with increase in the catalyst amount from 5 mg
(0.24 wt%) to 20 mg (0.95 wt%) resulting from the increase in num-
ber of active sites available. Thereafter the increase in the catalyst
amount does not show significant increase in the AGE conversion
suggesting that 0.95 wt% is adequate enough of F-ZIF-90 effective
for cycloaddition of AGE with CO2.
100
80
catalyst filtration
60
40
Conversion
The effects of reaction temperature on the synthesis of AGC were
studied using F-ZIF-90 catalyst at the semi-batch operation, and the
results are shown in Table 3. The conversion of AGE and the selec-
tivity to AGC increased as the temperature increased from 60 ◦C
to 120 ◦C. However, over 140 ◦C, the conversion remained nearly
constant and the selectivity decreased. Therefore, all the following
experiments were carried out at 120 ◦C. The main reaction byprod-
uct was 3-allyloxy-1,2-propanediol.
Selectivity
20
0
0
1
2
3
4
5
6
Time (h)
The effects of CO2 pressure on the reactivity of F-ZIF-90 at 120 ◦C
after 6 h of reaction in the semi-batch reactor are shown in Table 4.
The conversion of AGE increased as the CO2 pressure increased
Fig. 6. Time variant AGE conversion and selectivity of AGC for F-ZIF-90 under semi-
batch operation (AGE = 18.1 mmol, catalyst = 20 mg, T = 120 ◦C, reaction time = 6 h,
PCO = 1.17 MPa).
2
Please cite this article in press as: T. Jose, et al., Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the
cycloaddition of carbon dioxide to allyl glycidyl ether, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.05.022

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Table 5
5
Table 4
The effects of CO2 pressure on the reactivity of F-ZIF-90.
The reactivity of F-ZIF-90 for various epoxides.
PCO (MPa)
Conv. (%)
Sel. (%)
Yield (%)
Catalyst
Conv. (%)
Sel. (%)
Yield (%)
2
0.35
0.90
1.05
1.17
1.30
1.50
91.1
95.1
96.0
98.7
97.6
95.1
94.8
95.3
97.5
97.9
98.2
98.7
86.3
90.6
93.6
96.6
95.8
93.9
Styrene oxide
62.8
89.0
95.2
96.7
2.4
99.3
98.6
99.1
98.7
98.0
62.4
87.8
94.3
96.3
2.4
Propylene oxide
Epichlorohydrin
Phenyl glycidyl ether
Cyclohexene oxide
Reaction conditions: epoxide = 18.1 mmol, F-ZIF-90 = 20 mg (0.177 mol%), T = 120 ◦C,
reaction time = 6 h, PCO = 1.17 MPa, semi-batch operation.
Reaction conditions: AGE = 18.1 mmol, catalyst = 20 mg (0.177 mol%), T = 120 ◦C,
reaction time = 6 h, semi-batch operation.
2
of the quaternized glycine catalyst after DFT studies. The role of
F-ZIF-90 with the ether oxygen needs more detailed studies.
We compared the catalytic performance of the F-ZIF-90 with
other MOF-based heterogeneous catalysts reported in the literature
(Table 6). All the catalysts operated at relatively mild reaction con-
ditions (temperature 80–150 ◦C and CO2 pressure 0.7–2.02 MPa)
without using any co-catalyst and solvent except Co-MOF-74 which
used chlorobenzene as a solvent. The F-ZIF-90 exhibited the TON
superior to the best yields achieved so far by the different MOFs
[28,35,48–53].
Considering the above results and previous works [16,54–59]
we attempted to propose plausible mechanism (Scheme 2) includ-
ing the probable sequence of events occurred in the F-ZIF-90
catalyzed cycloaddition of CO2 with AGE, yielding AGC. The AGE
molecules approach the zinc metal atom, forming a metal oxygen
bonding with the epoxide ring, then nucleophilic anion (iodide ion)
on F-ZIF-90 is able to initiate an attack on the least hindered (␤) car-
bon atom of the epoxide ring. Ring opening of the epoxide occurs,
followed by formation of a new C I covalent bond. The ring-opened
epoxide moiety engages in attack with carbon dioxide, yielding an
alkyl carbonate anionic species, which eventually yields AGC upon
subsequent ring closure and catalyst regeneration.
Regarding the reusability of F-ZIF-90, the catalytic activity of the
recycled catalyst was evaluated at 120 ◦C under constant CO2 pres-
sure of 1.17 MPa for 6 h. In the recycle experiment, the used catalyst
was filtered, washed with acetone, and air dried before use. Fig S1
in the Supplementary information shows the XRD results of reused
catalyst and it confirmed the maintenance of its original structure
of F-ZIF-90 after use. However, the yield of AGC decreased from
96.6% (fresh) to 58.3% (recycled). The BET surface area decreased
from 763 to 548 m2/g after reuse. Miralda et al. [28] observed sim-
ilar trends, that is, decrease in both BET surface area and catalytic
activity as well as loss of the structural features upon further reuse
of ZIF-8 in the cycloaddition of CO2 to epichlorohydrin. They sug-
gested that a synergistic effect of the high pressure of CO2 and the
from 0.35 to 1.17 MPa. As CO2 is one of the reactant, the conver-
sion increased with higher concentration of CO2 resulted at higher
pressures. High CO2 pressure could enhance the absorption of CO2
in the solution of AGE. Zhang et al. [36] have reported an increase in
the solubility of CO2 in BMImPF6 by increasing CO2 pressure. It has
also been reported that high CO2 pressure increases the turnover
rate of the CO2/cyclohexene oxide coupling reaction catalyzed by
chromium salen complexes [16]. However, a decrease in the AGE
conversion and AGC selectivity was observed when the CO2 pres-
sure increased from 1.17 to 1.5 MPa. A similar pressure-dependence
trend has been observed in other catalytic systems [37–40]. Sun
et al. [40] suggested that the initial increase in yield at low CO2 pres-
sure was due to an increase in the CO2 concentration in the liquid
phase of the reaction system, but too high pressure would reduce
epoxide conversion because of lowered epoxide concentration in
the vicinity of the catalyst or the worse mixing of the reactants by
phase separation. Sun et al. [41] reported the two phases, a CO2-
rich gas phase and a liquid phase including epoxide, wherein CO2
is also soluble. The selectivity to AGC increased continuously when
the CO2 pressure increased from 0.35 to 1.5 MPa, since high CO2
pressure may inhibit the formation of byproducts or the backward
decomposition of AGC to AGE and CO2.
Various epoxide substrates were subjected to the cycloaddition
reaction using F-ZIF-90 under the optimized conditions determined
as explained above. The results are summarized in Table 5. All the
epoxides tested gave high conversions, with the exception of cyclo-
hexene oxide, which might be due to the high steric hindrance
caused by cyclohexene ring [42]. It was also observed that the epox-
ide substrates with an additional ether oxygen linkage in the side
chain (AGE and phenyl glycidyl ether), had higher catalytic activity
compared to other epoxide substrates. This extra edge in activity is
witnessed in many works concerned with epoxide CO2 cycloaddi-
tion reactions [10,43–47]. Our previous work [47], attributed this
high activity to the interaction of ether oxygen and COOH group
Table 6
Comparison of F-ZIF-90 with other MOF-based catalysts in the cycloaddition of CO2 and epoxides.
MOF
Epoxide
Cat. amounta (mol%)
T (◦C)
PCO (MPa)
Time (h)
Yield (%)
TONb
Ref.
2
Mg-MOF-74
ZIF-8
ZIF-8-f
SO
1.88
0.44
0.44
0.7
2.1
9.1
100
100
100
100
100
150
80
100
120
120
120
120
120
120
120
2
1
4
4
5
1
8
14
4
6
6
50
27
75
112
79
28
8
52
60
34
80
215
25
101
547
855
[48]
[28]
[28]
[49]
[50]
[51]
[34]
[52]
[38]
[38]
[38]
[53]
This work
This work
This work
EPCH
EPCH
SO
SO
SO
0.7
0.7
0.74
2
32.8
49.1
55
58
74
ZIF-8
UIO-66-NH2
MIL-68(In)NH2
Cr-MIL-101
Co-MOF-74
IRMOF-1
0.8
0.8
2.02
1.2
1.2
1.2
1.2
1.17
1.17
1.17
SO
1.2
1.6
62
96
SOc
AGE
AGE
AGE
AGE
AGE
AGE
AGE
0.59
0.55
0.43
1.6
0.430
0.177
0.088
20.1
44.1
92.3
40.7
43.4
96.6
75.1
IRMOF-3
F-IRMOF-3(BuI)
ZnHipBipy-B
ZIF-90
F-ZIF-90
F-ZIF-90
6
6
6
6
6
a
[(Moles of metal atom)/(moles of epoxide)] × 100 (%).
b
c
TON = moles of cyclic carbonate formed/moles of metal in MOF catalyst.
Chlorobenzene was used as a solvent.
Please cite this article in press as: T. Jose, et al., Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the
cycloaddition of carbon dioxide to allyl glycidyl ether, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.05.022

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Scheme 2. Proposed mechanism for the cycloaddition of CO2 and epoxide with F-ZIF-90.
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bonaceous products could be the reason of the activity loss and
crystalline instability of ZIF-8 after the reuse.
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and co-catalyst. The AGE yield showed maxima as the temperature
and CO2 pressure increased. However, the loss of its superior cat-
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Please cite this article in press as: T. Jose, et al., Functionalized zeolitic imidazolate framework F-ZIF-90 as efficient catalyst for the
cycloaddition of carbon dioxide to allyl glycidyl ether, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.05.022