In situ synthesis and encapsulation of copper phthalocyanine into MIL-101(Cr) and MIL-100(Fe) pores and investigation of their catalytic performance in the epoxidation of styrene

Article abstract of DOI:10.1142/S1088424619501323

In this work, copper phthalocyanine (CuPc) was encapsulated into mesocages of MIL-101(Cr) and MIL-100(Fe) by assembling CuPc's constitutional fractions using a deep eutectic solvent. The prepared materials, CuPc?MIL-101(Cr) and CuPc?MIL-100(Fe), were characterized by powder X-ray diffraction (PXRD), FT-IR, UV-vis and diffuse reflectance UV (DR-UV) spectroscopies, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ICP-OES spectrometry. The prepared materials were used as heterogeneous catalysts for catalytic epoxidation of styrene with molecular oxygen and also tert-butyl hydroperoxide (TBHP) as oxidants in acetonitrile as a solvent. The impact of MOFs and the role of the CuPc complex as the active species in the MOFs' cages in the epoxidation of styrene were investigated. Among the prepared catalysts, CuPc?MIL-101(Cr) showed the best performance. The heterogeneity of the catalysts was examined by a hot filtration test and ICP-OES of the filtrates after the reaction. Spent catalysts were analyzed by PXRD, FT-IR, UV-DRS, and TEM for reusability investigation and also to further explore the heterogeneous nature of the hybrid materials. Results showed that the prepared catalysts could be recycled and used for several concoctive times without a considerable drop in activity.

Full text of DOI:10.1142/S1088424619501323

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2019; 23: 1–14
DOI: 10.1142/S1088424619501323
Published at http://www.worldscinet.com/jpp/
In situ synthesis and encapsulation of copper phthalocyanine
into MIL-101(Cr) and MIL-100(Fe) pores and investigation
of their catalytic performance in the epoxidation of styrene
Ardeshir DadgarYeganeh, Mostafa M. Amini* and Nasser Safari◊
Department of Chemistry, Shahid Beheshti University, G.C., Tehran 1983963113, Iran.
Received 7 July 2019
Accepted 5 September 2019
ABSTRACT: In this work, copper phthalocyanine (CuPc) was encapsulated into mesocages of MIL­
1
01(Cr) and MIL­100(Fe) by assembling CuPc’s constitutional fractions using a deep eutectic solvent.
The prepared materials, CuPc@MIL­101(Cr) and CuPc@MIL­100(Fe), were characterized by powder
X­ray diffraction (PXRD), FT­IR, UV­vis and diffuse reflectance UV (DR­UV) spectroscopies, scanning
electron microscopy (SEM), transmission electron microscopy (TEM), and ICP­OES spectrometry.
The prepared materials were used as heterogeneous catalysts for catalytic epoxidation of styrene with
molecular oxygen and also tert­butyl hydroperoxide (TBHP) as oxidants in acetonitrile as a solvent.
The impact of MOFs and the role of the CuPc complex as the active species in the MOFs’ cages in the
epoxidation of styrene were investigated. Among the prepared catalysts, CuPc@MIL­101(Cr) showed
the best performance. The heterogeneity of the catalysts was examined by a hot filtration test and ICP­
OES of the filtrates after the reaction. Spent catalysts were analyzed by PXRD, FT­IR, UV­DRS, and
TEM for reusability investigation and also to further explore the heterogeneous nature of the hybrid
materials. Results showed that the prepared catalysts could be recycled and used for several concoctive
times without a considerable drop in activity.
KEYWORDS: MIL­101(Cr); MIL­100(Fe); metallophthalocyanine; epoxidation.
The use of Metal­Organic Frameworks (MOFs) in the
INTRODUCTION
field of heterogeneous catalysis has grown exponentially
over the last decade [8, 9]. Despite high concentrations
of metal centers with coordinately unsaturated or
exchangeable positions which can perform as catalytic
active sites, remarkable features such as high porosity
with regular pores and large surface areas, framework
flexibility, low framework density and large empty space,
have made MOFs promising candidates as solid matrices
for immobilization of transition metal complexes and
nanoparticles [10–14]. Among porous materials, MIL­
The selective epoxidation of styrene has attracted
notable attention in view of the fact that the epoxy
product is an essential intermediate in the synthesis of
pharmaceuticals and fine chemicals [1, 2]. Conven­
tionally, stoichiometric amounts of peracids like PhIO
have been used to perform epoxidation reactions, but
major disadvantages such as high cost, difficulty of
handling, lack of selectivity toward epoxy and formation
of unwanted wastes have led to serious environmental
and economic concerns [3, 4]. Thus, the epoxidation of
styrene by employing more benign and environmentally
friendly oxidants like molecular oxygen has been found
to be a promising alternative to the traditional route [5–7].
1
00 and MIL­101 MOFs are two examples of large non­
proteinic structures which have been designed so far and
used extensively both as catalysts and supports in liquid­
phase reactions such as catalytic oxidation [15–22]. These
MOFs circumvent some of the major drawbacks of their
counterparts in heterogeneous catalyzes, such as thermal
[23] and chemical [24] instability and lack of resistance
toward active site leaching under reaction conditions [25].
◊
SPP full member in good standing.
*
Correspondence to: Mostafa M.Amini, tel.: +98­21­29903109,
fax: +9­21­22431663, email: m­pouramini@sbu.ac.ir.
Copyright © 2019 World Scientific Publishing Company

2
A. D. YEGANEH ET AL.
Scheme 1. Schematic representation of CuPc synthesis within the pores of MIL­101(Cr) or MIL­100(Fe)
Immobilization of polyoxometalates into MIL­100(Fe)
and MIL­101(Cr) has provided highly efficient and
stable heterogeneous catalysts for epoxidation of alkenes
and benzyl alcohol oxidation, respectively [26, 27].
Other metal complexes and metal nanoparticles have
also been incorporated within the cages of the earlier
mentioned MOFs in order to catalyze various organic
transformations [28–32].
The activity of coordination complexes as homo­
geneous catalysts is well established [33–35], but
from an industrial point of view, the heterogenization
of homogeneous catalysts by immobilizing them into
appropriate solid support provides easy recovery and
reusability as two significant advantages of this approach
process alongside a grueling work­up has limited this
method. The catalytic activity of the constructed material
by a new strategy was examined in the epoxidation of
styrene with TBHP as the oxidant, and 72% conversion
with 65% selectivity to styrene oxide was obtained.
Recently, Boroujeni et al. reported a straightforward and
green procedure to encapsulate MPcs by loading their
constituents inside the internal voids of MIL­101 and
then employing an ionic liquid to synthesize the desired
MPc@MIL­101 [44].
Herein, we further investigate the potential of the
reportedstrategyforencapsulatingcopperphthalocyanine
(CuPc) inside the pores of MIL­100(Fe) as well as
MIL­101(Cr) using deep eutectic solvent (DES) which
recently has been reported by Shaabani et al. [45] to
synthesize MPc complexes in a shorter reaction time
and at a lower temperature than conventional routes. The
obtained materials have been characterized by PXRD,
[
(
36, 37]. In this context, phthalocyanine metal complexes
MPcs), which are a substantial class of coordination
compounds, have become the center of attention in past
decades due to their facile large­scale preparation and
chemical and thermal stability. These factors make MPcs
great candidates as catalysts, especially in oxidation
reactions [38]. Different strategies, including electrostatic
interaction [39], covalent anchoring [40], impregnation,
and encapsulation inside porous structures have been
applied for immobilization of MPcs in supports. The
impregnation approach is limited because of MPcs’ low
solubility in common organic solvents; this consequently
necessitates the usage of substituted MPcs which are
soluble but challenging to synthesize such as FePcS and
RuPcF16 that are encapsulated inside MIL­101(Cr) via
this method and used in oxidation reactions [41, 42]. In
FT­IR, UV­Vis, UV­DRS, SEM, TEM and N adsorption–
2
desorption techniques. The catalytic performance and
heterogeneity of the prepared catalysts in the styrene
epoxidation with O2 and aqueous TBHP have also
been studied. Scheme 1 illustrates in situ synthesis
and encapsulation of copper phthalocyanine into MIL­
101(Cr) and MIL­100(Fe).
RESULTS AND DISCUSSION
Characterization of precursors and catalysts
2
014, Ma and coworkers introduced a new strategy to
The synthesis of MIL­101(Cr) and MIL­100(Fe) was
confirmed by powder X­ray diffraction (PXRD) analysis
(Figs 1 and 2). The diffraction patterns are well matched
encapsulate CoPc into the pores of bio­MOF [43], but
a requirement to use anionic MOF and a long reaction
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In situ SYNTHESIS AND ENCAPSULATION OF COPPER PHTHALOCYANINE INTO MIL-101(Cr) AND MIL-100(Fe) PORES
3
2
+
Fig. 3. FT­IR spectra of (a) MIL­101(Cr), (b) Cu ­
phthalonitrile@MIL­101(Cr) and (c) CuPc@MIL­101(Cr)
Fig. 1. PXRD patterns of (a) Simulated MIL­101(Cr), (b) As­
synthesized MIL­101(Cr) and (c) CuPc@MIL­101(Cr)
2
+
Fig. 4. FT­IR spectra of (a) MIL­100(Fe), (b) Cu ­
phthalonitrile@MIL­100(Fe) and (c) CuPc@MIL­100(Fe)
Fig. 2. PXRD patterns of (a) Simulated MIL­100(Fe), (b) As­
synthesized MIL­100(Fe) and (c) CuPc@MIL­100(Fe)
of the aromatic ring [49]. After loading of phthalonitrile
2
+
to the simulated ones which were obtained from their
crystallographic information files (CIFs). As is shown,
the synthesis of CuPc inside the pores of MIL­100(Fe)
and MIL­101(Cr) did not affect the reflections of these
MOFs, indicating that their structural integrities are
maintained. Since the characteristic reflections of free
CuPc complex according to ICDD card no. 11­0893
were not detected in diffractograms, it can be assumed
that the CuPc is highly dispersed inside the pores of the
MOFs [44].
into Cu @MIL­100(Fe) and MIL­101(Cr), a band
­1
around 2230 cm appears in their spectrum which is
ascribed to CN stretching vibration (Figs 3b and 4b),
but after the cyclotetramerization of phthalonitrile this
band disappeared, which can corroborate the successful
synthesis of CuPc inside the MOFs [44, 50]. Other weak
bands at 1087, 1118, and a shoulder near 1334 cm ,
which are the characteristic vibrations of CuPc, can be
seen in the FT­IR spectrum of CuPc@MIL­101(Cr) and
CuPc@MIL­100(Fe) (Figs 3c and 4c) [51].
­1
The FT­IR spectrum of MIL­101(Cr) (Fig. 3a) reveals
characteristic vibrational bands of the framework
O–C–O at 1398 and 1612 cm , which corresponds to the
asymmetric andsymmetric stretchingmodes, respectively
To investigate the encapsulation of CuPc within the
pores of MIL­101(Cr), and MIL­100(Fe), CuPc was
extracted from MIL­101(Cr) and MIL­100(Fe) and
their UV­vis was recorded. As Fig. 5 shows, the spectra
­
1
[
1
1
46]. Also, a benzene ring C=C, stretching vibration at
demonstrate two absorption bands at 702 and 795 nm,
­
1
*
508 cm , and C–H deformation vibrations at 1157,
arising from p→p charge transfer from a1g to e
g
­
1
018, and 748 cm are observed in the spectrum [47].
orbitals, known as Q bands [52, 53]. Those bands are the
characteristic bands of CuPc in concentrated sulfuric acid.
They appeared after extraction of CuPc from the MOFs
and are ascribed to planar D4h symmetry in solutions [54].
Moreover, an absorption band became visible at around
Typical characteristic bands of MIL­100(Fe) (Fig. 4a)
­
1
at 1627, 1450, and 1370 cm are allocated to C=O
stretching vibration and asymmetrical and symmetrical
vibrations of O–C–O carboxylate group, respectively
­1
[
48]. Moreover, the bands at 760 and 710 cm in the
440 nm, known as the Soret or B band, and is attributed
*
fingerprint region are assigned to C–H bending vibrations
to another ligand centered p→p transition from a2u to e
g
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4
A. D. YEGANEH ET AL.
Fig. 5. UV­vis spectra of (a) Extracted CuPc from MIL­101(Cr), (b) Extracted CuPc from MIL­100(Fe)
Fig. 6. UV­DR spectrum of (a) MIL­101(Cr), (b) CuPc@MIL­
01(Cr) and (c) Neat CuPc complex
Fig. 7. UV­DR spectrum of (a) MIL­100(Fe), (b) CuPc@MIL­
100(Fe) and (c) Neat CuPc complex
1
orbitals [52–54]. Therefore, it can be concluded that the
CuPc remained intact after encapsulation in the MOFs.
The presence of CuPc inside the MOFs is also
confirmed by diffuse reflectance UV­vis spectroscopy, as
shown in Figs 6 and 7. Neat CuPc complex displayed
broadened and resolved bands in the 550–750 nm region,
indicating a non­planar geometry for the complex.
After accommodation of CuPc inside the pores of MIL­
sizes of MIL­101(Cr) (300–600 nm) and MIL­100(Fe)
(200–500 nm) were unaltered after incorporation of
CuPc molecules, although a low extent of agglomeration
of particles was observed in the case of CuPc@MIL­
100(Fe) (Fig. 8d). TEM images further confirm that
the shape and size of the MOF particles were retained
after the encapsulation of CuPc complexes inside their
structures (Figs 8e and 8f).
1
6
00(Fe) and MIL­101(Cr), those bands shifted to around
80 and 610 nm and can be assigned to Q(0,0) and
The N adsorption–desorption isotherms of bare and
2
CuPc­encapsulated MOFs are given in Figs 9 and 10.
Both MIL­101(Cr) and CuPc@MIL­101(Cr) revealed
type I(b) isotherms with H4 hysteresis loops, which
are exhibited in the presence of micropores and narrow
mesopores, according to IUPAC classification [57].
MIL­100(Fe) and CuPc@MIL­100(Fe) also displayed
H4 hysteresis loops with mixed type I/IV isotherms,
and they related to materials with microporous windows
and mesoporous cages [58]. The textural parameters of
the prepared materials are shown in Table 1. The BET­
specific surface area and pore volume of MIL­101(Cr)
Q(0,1) transitions of monomeric and dimeric species,
respectively. The red shift and reduction of split bands
after the encapsulation of CuPc inside the MOFs suggests
that the CuPc molecules are highly dispersed and within
the MOFs cavities [54–56].
SEM images were taken to investigate the morphology
and structure of the MOFs before and after the
encapsulation of CuPc complexes. As revealed in Fig. 8,
the structures of MIL­100(Fe) and MIL­101(Cr) remained
intact after encapsulation of CuPc molecules inside their
pores, confirming that the preparation process does
not affect the MOFs’ structures. Furthermore, particle
2
­1
3
­1
are 2437 m g and 1.15 cm g , and for MIL­100(Fe) are
2
­1
3
­1
1248 m g and 0.72 cm g , respectively. These values
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In situ SYNTHESIS AND ENCAPSULATION OF COPPER PHTHALOCYANINE INTO MIL-101(Cr) AND MIL-100(Fe) PORES
5
Fig. 8. SEM images of (a) MIL­101(Cr), (b) CuPc@MIL­101(Cr), (c) MIL­100(Fe) and (d) CuPc@MIL­100(Fe). TEM images of
e) CuPc@MIL­101(Cr) and (f) CuPc@MIL­100(Fe)
(
2
­1
3
­1
decreased to 2262 m g and 0.91 cm g after incor­
Catalytic studies
2
­1
poration of CuPc in MIL­101(Cr), and to 1104 m g
3
­1
The catalytic activity of the prepared solids was
investigatedintheepoxidationofstyreneintwooptimized
reaction conditions: one with O as oxidant and iso­
butyraldehyde as co­reductant (Table 2), and the other
with aqueous TBHP as oxidant (Table 3) in acetonitrile
media. At first, the reaction in the absence of catalyst
was performed in both systems, and low conversions of
styrene were observed (Tables 2 and 3, entry 1). These
results indicate the importance of catalysts’ role in the
and 0.55 cm
g
after inclusion in MIL­100(Fe),
respectively. The decrease of specific surface areas and
pore volumes of the encapsulated samples indicates the
presence of CuPc complexes within the cavities of the
MOFs. The amount of CuPc in the pores of MIL­100(Fe)
and MIL­101(Cr) was obtained by ICP­OES, and a value
of 10.1 and 17.5 wt.% loading was acquired for CuPc@
MIL­100(Fe) and CuPc@MIL­101(Cr), respectively
2
(
Table 1).
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6
A. D. YEGANEH ET AL.
Fig. 9. N adsorption­desorption isotherms of (a) MIL­101(Cr)
Fig. 10. N adsorption­desorption isotherms of (a) MIL­100(Fe)
2
2
and (b) CuPc@MIL­101(Cr)
and (b) CuPc@MIL­100(Fe)
reaction progression. The reaction with activated MIL­
demonstrated activity in the epoxidation of styrene with
49.8% conversion and 55.3% selectivity to the epoxy
product with molecular oxygen as oxidant (Table 2,
entry 4). The catalytic activity of the MOFs was also
1
5
01(Cr) in the O /iso­butyraldehyde system resulted in
3.4% styrene conversion with 72.4% selectivity towards
2
styrene oxide (Table 2, entry 3). Moreover, MIL­100(Fe)
Table 1. Textural properties and the amount of CuPc in the samples
2
­1
3
­1
a
b
Samples
SBET (m g )
VTotal (cm g )
CuPc content (wt.%)
MIL­101(Cr)
CuPc@MIL­101(Cr)
MIL­100(Fe)
2437
2262
1248
1104
1.15
0.91
0.72
0.55
—
17.58
—
CuPc@MIL­100(Fe)
10.1
a
b
VTotal was measured at P/P = 0.98. Determined by ICP­OES.
0
a
Table 2. catalyst screening in the epoxidation of styrene using O as oxidant
2
Entry
1
Catalyst
Conversion (%)
Selectivity (%)
B
b
SO
OP
No catalyst
10.6
52.5
53.4
49.8
100
47.2
63.6
72.4
55.3
85
33.2
23.1
19.2
27.6
9.1
19.6
13.3
13.4
17.1
5.9
c
2
CuPc
d
3
MIL­101(Cr)
d
4
MIL­100(Fe)
5
6
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
82.8
100
76.8
80.6
75.2
10.3
10
12.9
9.4
e
7
f
8
80.1
8.1
16.7
a
Reaction conditions: styrene (1 mmol), catalyst (0.15 mol% based on Cu), CH CN (2 ml), O balloon (1 atm),
3
2
b
iso­butyraldehyde (3 mmol), temperature (60 °C), time (4 h). Other products including phenylacetaldehyde and benzoic
acid. 0.8 mg CuPc was used. 5 mg MOF was used. 4th run. 3rd run.
c
d
e
f
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In situ SYNTHESIS AND ENCAPSULATION OF COPPER PHTHALOCYANINE INTO MIL-101(Cr) AND MIL-100(Fe) PORES
7
a
Table 3. catalyst screening in the styrene epoxidation using TBHP as oxidant
Entry
1
Catalyst
Conversion (%)
17.1
Selectivity (%)
B
b
SO
OP
No catalyst
35.3
46.3
18.5
c
2
CuPc
66.8
45.9
36.2
100
90.7
100
89
61.3
38.4
17.2
42.9
29.6
45.6
29.9
28.8
40.3
32.4
51.4
50.2
50.9
54.1
47.3
54.2
53.4
44.7
6.3
10.2
32.6
6.2
d
3
MIL­101(Cr)
d
4
MIL­100(Fe)
5
6
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
16.2
7.1
e
7
e
8
13.9
17.7
15
f
9
61.1
50.3
f
1
0
a
Reaction conditions: styrene (1 mmol), catalyst (0.15 mol% based on Cu), CH CN (2 ml), TBHP 70% (3 mmol), temperature
3
b
c
d
(
80°C), time (7 h). Other products including phenyl acetaldehyde and benzoic acid. 0.8 mg CuPc was used. 5 mg MOF
e f
was used. 3rd run. Reaction was performed at 60°C for 4 h (identical to the reaction condition with molecular oxygen as
the oxidant).
seen in the presence of TBHP as oxidant with relatively
lower conversions and selectivity toward styrene oxide
conversion and 76.1% selectivity to the epoxy product
(Table 2, entry 6) in the O /iso­butyraldehyde system.
2
(
Table 3, entries 3 and 4). The catalytic behavior of the
The high catalytic activity of the resulting catalysts can
be justified not only by the intrinsic catalytic activity
of MIL­100(Fe) and MIL­101(Cr) due to the presence
of active catalytic sites as mentioned above but also by
their excellent physical properties such as high surface
area and pore volumes. Those textural parameters make
them suitable supports for both encapsulating the CuPc
complex as another active catalytic species and allowing
the diffusion of guest molecules and the emergence of
the products [17, 58, 61]. Although CuPc@MIL­101(Cr)
and CuPc@MIL­100(Fe) exhibit high styrene conversion
using TBHP as oxidant, benzaldehyde was the main
product and the selectivity was lower in general than the
bare MOFs in epoxidation reactions can be explained by
the existence of coordinatively unsaturated sites (CUS)
of Cr(III) in MIL­101(Cr) and the presence of Fe(III)/
Fe(II) Lewis acid pairs in MIL­100(Fe), which can act
as catalytic active sites [59, 60]. The reaction with the
neat CuPc complex was also carried out in each oxidative
system for comparison, and its results are shown in
Tables 2 and 3, entry 2. After encapsulation of CuPc by
assembling inside the pores of MIL­101(Cr) and MIL­
1
00(Fe), conversion and selectivity of the resulting
catalysts were conspicuously increased, especially in
the reaction with O and iso­butyraldehyde, in which
2
the catalysts were more selective to styrene oxide.
The reaction with CuPc@MIL­101(Cr) showed 100%
conversion and 85% selectivity to styrene oxide (Table 2,
entry 5), while CuPc@MIL­100(Fe) exhibited 82.8%
reaction with O and iso­butyraldehyde (Table 3, entries 5
and 6). With TBHP as oxidant, the reaction was also
carried out under the same experimental conditions as a
2
function of time and temperature to O /iso­butyraldehyde
2
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A. D. YEGANEH ET AL.
system, and lower conversions and selectivities were
obtained (Table 3, entries 9 and 10). These results suggest
hours for the reactions to complete, while in the reactions
with TBHP seven hours were needed for the catalysts to
accomplish the best conversions.
that the reaction with O /iso­butyraldehyde system was
2
more efficient than the reaction with TBHP as oxidant.
Since TBHP is very toxic and not eco­friendly, therefore,
molecular oxygen is an appropriate oxidant in the styrene
epoxidation over the prepared catalysts. A possible
reason for the lower conversion and selectivity in the
case of CuPc@MIL100(Fe) could be explained by the
smaller pore windows of MIL­100(Fe) (5.5 and 8.6 Å)
compared to MIL­101(Cr) (16 and 19 Å), which restrict
the diffusion of substrate to reach internal pores and
cavities where CuPc­active sites are located [16, 20].
The evolvement of the conversion of styrene as a
function of reaction time employing CuPc@MIL­101(Cr)
and CuPc@MIL­100(Fe) in both oxidative systems was
evaluated, and results are presented in Fig. 11. As can be
The influence of different substituents, including
electron­donating and withdrawing groups in styrene,
have been further investigated in the epoxidation reaction
with O /iso­butyraldehyde system under optimized
2
reaction conditions (Table 4). The reaction with electron­
withdrawing 4­chloro and 4­nitro moieties resulted in
lower conversions and selectivity toward styrene oxide
for both catalysts. However, in the case of electron­
donating 4­methyl and 4­methoxy substituents, the
epoxidation reaction in the presence of CuPc@MIL­
101(Cr) as catalyst was completed in a shorter reaction
time compared to the bare styrene, but when CuPc@MIL­
100(Fe) was used as catalyst, although the conversions
did not improve, the selectivity to the epoxy product was
increased. From these results, it can be concluded that the
seen, for the O /iso­butyraldehyde system, it takes four
2
Fig. 11. Epoxidation of styrene catalyzed by CuPc@MIL­101(Cr) and CuPc@MIL­100(Fe) using (a) O as oxidant and (b) TBHP
2
as oxidant
a
Table 4. Epoxidation of styrene derivatives with molecular oxygen
b
Substrate
Styrene
Catalyst
Conversion (%)
Selectivity (%)
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
100
82.8
86.5
75.2
84
85
76.8
64
4
4
4
­Chlorostyrene
­Nitrostyrene
62.6
71.3
50.1
88.4
85.2
85.7
79.2
68.9
100
80.7
100
73.7
c
CuPc@MIL101(Cr)
­Methylstyrene
­Methoxystyrene
CuPc@MIL­100(Fe)
d
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
4
a
Reaction conditions: styrene (1 mmol), catalyst (0.15 mol% based on Cu), CH CN (2 ml), O
3
2
b
balloon (1 atm), iso­butyraldehyde (3 mmol), temperature (60°C), time (4 h). Selectivity to Styrene
Oxide. Reaction completed after 2.5 h. Reaction completed after 3 h.
c
d
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In situ SYNTHESIS AND ENCAPSULATION OF COPPER PHTHALOCYANINE INTO MIL-101(Cr) AND MIL-100(Fe) PORES
Table 5. Styrene epoxidation over various metallophthalocyanine­based heterogeneous catalysts
9
a
Entry
Catalyst
Oxidant
Conversion (%)
Selectivity (%)
Ref.
SO
39.1
74
B
43.5
18
1
2
3
4
5
6
7
8
9
CuPcY­1(e)
TBHP
94.2
99
[71]
[72]
FePc@SiO2
Air/Iso­butyraldehyde
CuPcCl .NH ­MCM­41
TBHP
46.8
100
72
25
19
[2]
16
2
CuPcCl .NH ­MCM­41
O /Iso­butyraldehyde
2
74.4
65
20
[2]
16
2
Co­Pc@bio­MOF­1
CuPcS@MC
TBHP
TBHP
TBHP
—
[43]
50
—
—
[73]
ZnTAPc/Gr
73
84
—
[74]
CoPcTs­Zn Al­LDH
O /Iso­butyraldehyde
2
100
81
90
10
[75]
2
CuPcTs­Zn Al­LDH
O /Iso­butyraldehyde
2
86
—
[75]
2
1
1
1
1
1
0
1
2
3
4
ZnPc­MWCNTs
TBHP
TBHP
TBHP
96.6
100
90.7
100
82.8
86.1
42.9
29.6
85
10.9
50.2
54.1
9.1
10.3
[76]
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
This work
This work
This work
This work
O /Iso­butyraldehyde
2
O /Iso­butyraldehyde
76.8
2
a
Experimental details and information about catalysts’ structures are given in the references.
electron­donating groups on styrene prompted the double
bond to be activated more readily by the enhancement of
electron density, as suggested in the literature [62, 63].
Nevertheless, the steric hindrance of methyl and methoxy
groups could limit the diffusion of substrates into the
voids of CuPc@MIL­100(Fe) and therefore cause the
conversions to be decreased compared to the styrene
alone.
Table 5 summarizes the results of various MPc­based
heterogeneous catalysts in the epoxidation of styrene. It
is apparent that the CuPc­encapsulated MOFs used in this
study demonstrate comparable results from the catalytic
activity point of view, particularly in the case of the O2/
iso­butyraldehyde oxidative system, where the catalysts
were also selective toward the desirable product, styrene
oxide. Although the catalysts in this study exhibited high
styrene conversion when TBHP was used as the oxidant,
the selectivity was poor compared to other catalysts listed
in Table 4. All supports used previously to immobilize
MPcs were inactive themselves, however, in this work the
MOFs were catalytically active and showed a synergistic
effect with CuPc as catalytically active phases in styrene
epoxidation. In addition, prior functionalization of the
support or substitutions of the MPc were also necessary
for most of the reported catalytic systems.
Recyclability and heterogeneity of the catalysts
The recyclability and stability of the catalyst are
essential properties of heterogeneous catalyst from
economic and environmental points of view. CuPc@
MIL­101(Cr) was successively recovered four times in
the styrene epoxidation using O and iso­butyraldehyde
2
without a noticeable reduction in conversion, although
the selectivity toward styrene oxide was slightly
decreased in the fourth run (from 85% to 80.6%)
(Fig. 12a). The recyclability of CuPc@MIL­101(Cr)
was also tested with TBHP as oxidant, and the catalyst
was recovered three times without significant loss of
activity (Fig. 12b). The reusability experiment was also
carried out for CuPc@MIL­100(Fe) in the presence of
both O /iso­butyraldehyde and TBHP as oxidants, and
2
the results showed that this catalyst could be recovered
for three cycles in both oxidative systems (Figs 12c
and 12d). The PXRD patterns of the recycled catalysts
indicate that the structural integrity of the catalysts was
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 9–14

10
A. D. YEGANEH ET AL.
Fig. 12. Recyclability of CuPc@MIL­101(Cr) in the styrene epoxidation with (a) O as oxidant and (b) TBHP as oxidant, and
2
CuPc@MIL­100(Fe) with (c) O as oxidant and (d) TBHP as oxidant
2
Table 6. The amount of leached metals in the reaction solution determined by
ICP­OES
Catalyst
Oxidant
Metal content (ppm)
Cu
0.3
Cr
0.03
0.44
—
Fe
—
O /iso­butyraldehyde
2
CuPc@MIL­101(Cr)
CuPc@MIL­100(Fe)
TBHP
0.8
—
O /iso­butyraldehyde
2
0.75
1.13
~
-1
TBHP
—
1.92
preserved after consecutive runs (Figs S1–S2, Supporting
information). The FT­IR spectra of the catalysts after
final runs demonstrated that the characteristic bands
of the samples were also maintained (Figs S3–S4).
The UV­DR spectra of the spent catalysts exhibited no
significant shifts of absorption peaks, although in the case
of recovered CuPc@MIL­101(Cr) in the reaction with
TBHP as oxidant and recovered CuPc@MIL­100(Fe)
in both oxidative systems, the broadening of absorption
bands was observed which is attributed to aggregation of
the CuPc complex (Figs S5–S6) [64]. The TEM images
observed after the catalytic reactions with both TBHP and
O /iso­butyraldehyde displayed no significant changes in
2
the catalysts’ shapes and morphology (Fig. S7).
The investigation of heterogeneity of the catalysts was
conducted by hot filtration tests and the reaction solution
was analyzed by ICP­OES after removing the catalysts to
examine possible leaching of transition metals. Table 6
shows the amount of metals leached into the reaction
media.As can be observed, the amounts of leached metals
are below or around 1 ppm in the reaction with O and
2
TBHP as oxidants, respectively. It is worth mentioning
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 10–14

In situ SYNTHESIS AND ENCAPSULATION OF COPPER PHTHALOCYANINE INTO MIL-101(Cr) AND MIL-100(Fe) PORES
11
Fig. 13. Hot filtration tests of (a) CuPc@MIL­101(Cr) with O as oxidant, (b) CuPc@MIL­101(Cr) with TBHP as oxidant,
2
(
c) CuPc@MIL­100(Fe) with O as oxidant and (d) CuPc@MIL­100(Fe) with TBHP as the oxidant in the styrene epoxidation
2
that such amounts of leached metal are acceptable in the
production of fine chemicals [65]. Hot filtration tests
were also carried out in both oxidative systems, and the
results are shown in Fig. 13. The catalysts were filtered
(DES) was prepared by a previously reported procedure
[66]. Copper phthalocyanine (CuPc) was also synthesized
by a recently described method [45] from a mixture of
copper(II) chloride salt and phthalonitrile in the presence
of DES and employed as the homogeneous catalyst for
comparison.
off after 30 min in the reaction with O /iso­butyraldehyde
2
and after two hours in the case where TBHP was the
oxidant. After removing the catalysts, the progress of
each reaction was dramatically decreased; this confirms
the heterogeneous route of the reaction.
Characterizations
The powder X­ray diffraction (PXRD) patterns
were collected on an STOE diffractometer using Cu
EXPERIMENTAL
K radiation (l = 1.5418 Å). The FT­IR spectra were
a
measured on a Bomem MB­Series FT­IR spectrometer
using the KBr pellet method. The Cu contents in the
compounds were obtained using an inductively coupled
plasma­optical emission spectrometer (ICP­OES) with
a Varian Vista­PRO instrument. The UV­vis spectra
of the materials were determined with a Shimadzu
UV­2100 spectrophotometer. The diffuse reflectance
UV spectra were acquired on a Shimadzu UV­2550
spectrophotometer. The scanning electron microscopy
images were obtained with a Hitachi SU3500 scanning
electron microscope. TEM images were taken by a Philips
Materials
All compounds were not purified and used as
.
.
purchased. Cr(NO ) 9H O, CuCl Fe(NO ) 9H O,
3
3
2
2,
3 3
2
tert­butyl hydroperoxide (TBHP) 70% aqueous solution,
terephthalic acid (TPA) and styrene were acquired from
Merck. Trimesic acid (H BTC), iso­butyraldehyde,
choline chloride, and urea were procured from Sigma–
Aldrich. All the solvents were of analytical grade and
obtained from Daejung Chemicals. Deep eutectic solvent
3
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 11–14

12
A. D. YEGANEH ET AL.
CM30 scanning transmission electron microscope.
Nitrogen adsorption­desorption isotherms were recorded
at ­196°C with a BELSORP­Mini II high precision
surface area and pore size analyzer. The samples were
degassed at 150°C for 12 h prior measurements. The
specific surface area was calculated by the Brunner–
Emmet–Teller (BET) equation.
Synthesis of CuPc@MIL-101(Cr)
and CuPc@MIL-100(Fe)
2
+
To200mgofdriedCu @MIL­101(Cr),2mlofethanol
was added and briefly sonicated. Then, phthalonitrile
(0.492 mmol) was added to the suspension and stirred
for 1 h. After that, ethanol was removed under reduced
pressure, and 2 ml of DES was added to the resulting
solid. Afterward, the mixture was heated to 150°C for
Preparation of MIL-101(Cr)
3
0 min to obtain CuPc@MIL­101(Cr) as revealed by
MIL­101(Cr) was synthesized based on a reported
hydrofluoric acid (HF)­free procedure [67]. Briefly, a
the deep blue color of the as­prepared catalyst. CuPc@
MIL­100(Fe) was prepared by the same procedure except
that 0.400 mmol phthalonitrile in ethanol was added to
the Cu @MIL­100(Fe) suspension, and the resulting
mixture was stirred for 3 h. The synthesized catalysts
were dried and activated under vacuum at 150°C
overnight before the catalytic run.
.
mixture of Cr(NO ) 9H O (5 mmol), TPA (5 mmol),
3
3
2
2
+
and deionized (DI) water (20 mL) was dispersed by
short sonication. Then the suspension was placed in
a hydrothermal autoclave reactor and kept for 18 h at
2
18°C. The green solid was collected by centrifugation,
washed with distilled water and acetone, and soaked in
0 ml DMF at 70°C for 12 h to eliminate any unreacted
2
Catalytic test
linker trapped within the pores. The resulting material
was separated by centrifuge, washed with methanol
and acetone, and dried under vacuum at 150°C for 12 h
before further use.
The catalytic styrene epoxidation was carried out in a
1
0 ml PTFE screw cap glass vial with septa. In a typical
experiment, styrene (1 mmol), catalyst (0.15 mol% based
on Cu) and iso­butyraldehyde (3 mmol) were added
to acetonitrile (2 ml) as the solvent. Subsequently, an
oxygen balloon was placed at the top of the glass vial,
and the reaction mixture was heated to 60°C for 4 h.After
the reaction was completed, the catalyst was recovered
by centrifuge, washed thoroughly with acetonitrile and
dried at 150°C under reduced pressure for 12 h before
the next run. The products were examined with a gas
chromatograph (Agilent 7890A) equipped with a BP­5
capillary column and an FID detector. The reaction with
TBHP 70% was carried out, except 3 mmol of TBHP was
Preparation of MIL-100(Fe)
MIL­100(Fe) was prepared in an HF­free solution,
according to the procedure described in the literature [68].
.
Firstly, Fe(NO ) 9H O (18 mmol) was added to 18 ml
3
3
2
DI water and stirred until fully dissolved. Then, H BTC
3
(12 mmol) was added, and the mixture was stirred for 1 h.
The obtained mixture was transferred into an 80 mlTeflon­
lined stainless steel autoclave and kept at 160°C for 15 h.
After cooling down the autoclave to room temperature,
the orange solid was collected by centrifugation, washed
with 180 ml water at 70°C for 3 h and then 180 ml
ethanol at 65°C for another 3 h. The obtained powder
was recovered by centrifuge, dried at 80°C overnight and
then at 150°C under vacuum for 12 h before use.
used instead of the O balloon and reductant.
2
CONCLUSIONS
In summary, copper phthalocyanine (CuPc) complex
was synthesized and encapsulated inside the pores of
MIL­100(Fe) and MIL­101(Cr) with a more convenient
approach than the reported strategies utilizing deep
eutectic solvent (DES) in shorter reaction time and lower
temperature. The prepared materials were employed as
heterogeneous catalysts in the epoxidation of styrene
2
+
Preparation of Cu @MIL-101(Cr)
2
+
and Cu @MIL-100(Fe)
2
+
The loading of Cu inside the pores of MIL­100(Fe)
and MIL­101(Cr) was done via a double­solvent approach
69, 70]. Typically, 200 mg of activated MIL­101(Cr)
[
was suspended in 40 ml dry n­hexane as a hydrophobic
solvent and sonicated for 25 min until homogeneous
suspension achieved. 0.123 ml of 1 M aqueous solution
with O and aqueous TBHP as oxidants in two optimized
2
reaction conditions. The catalysts demonstrated excellent
catalytic activity, especially with molecular oxygen as a
green oxidant with high conversion (100% with CuPc@
MIL­101(Cr) vs. 82.8% with CuPc@MIL­100(Fe)) and
selectivity toward styrene oxide (85% with CuPc@
MIL­101(Cr) vs. 76.8% with CuPc@MIL­100(Fe))
as the desired product. Moreover, the catalysts can be
recovered and reused several times without considerable
drops in activity, and they also are stable after reuse
as demonstrated by PXRD, FT­IR, and UV­DRS
techniques. Finally, the leaching experiments, combined
of CuCl as a hydrophilic solvent was added dropwise
2
under constant intense stirring. After continuous stirring
for 3 h, the obtained powder was recovered and dried in
vacuum at 150°C for 12 h. In the case of MIL­100(Fe),
the same procedure was employed except the amount
of added CuCl solution added was 0.100 ml, since
2
the total pore volume of the MIL­100(Fe) was smaller
than MIL­101(Cr) as revealed by nitrogen adsorption
measurements.
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 12–14

In situ SYNTHESIS AND ENCAPSULATION OF COPPER PHTHALOCYANINE INTO MIL-101(Cr) AND MIL-100(Fe) PORES
13
with ICP­OES results, illustrated that the catalysts are
genuinely heterogeneous.
17. Hong DY, Hwang YK, Serre C, Férey G and Chang
JS. Adv. Funct. Mater. 2009; 19: 1537–1552.
1
8. Hwang YK, Hong DY, Chang JS, Jhung SH,
Seo YK, Kim J, Vimont A, Daturi M, Serre C
and Férey G. Angew. Chem., Int. Ed. 2008; 47:
Acknowledgments
The authors thank the Vice­President’s Office for
Research Affairs of the Shahid Beheshti University for
supporting this work.
4
144–4148.
1
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Supporting information
Characterizations of spent catalysts (Figs S1–S7) are
given in the supplementary material, which is available
free of charge via the internet at http://www.worldscinet.
com/jpp/jpp.shtml.
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