Mg-porphyrin complex doped divinylbenzene based porous organic polymers (POPs) as highly efficient heterogeneous catalysts for the conversion of CO2 to cyclic carbonates

Article abstract of DOI:10.1039/c8dt02913j

A series of Mg-porphyrin complex doped divinylbenzene (DVB) based porous organic polymers (POPs) were systematically afforded through the method of free radical polymerization under solvothermal conditions. These POP catalysts have physical advantages of

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

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Mg-Porphyrin complex doped divinylbenzene based porous
organic polymers (POPs) as highly efficient heterogeneous
catalysts for the conversion of CO2 to cyclic carbonates
Received 00th January 20xx,
Accepted 00th January 20xx
Wenlong Wang,*a Cunyao Li,b Jutao Jin,a Li Yan,b Yunjie Ding*b
DOI: 10.1039/x0xx00000x
A series of Mg-porphyrin complex doped divinylbenzene (DVB) based porous organic polymers (POPs) were systematically
afforded through the method of free radical polymerization under solvothermal conditions. These POPs catalysts have
physical advantages of high surface areas, hierarchical pore structures, high thermal stability and spatially separated active
Mg-porphyrin sites, which leads to very high efficiency in the conversion of CO2 to cyclic carbonates with the aid of tetra-n-
butyl ammonium bromide (TBAB) as a nucleophile. The effect of doping ratio (Mg-porphyrin complex to DVB) towards
catalytic efficiency was studied and discussed, and detrimental embedding effect was found. The effect of reaction
temperature and pressure on catalytic activity as well as other epoxide substrates were also examined fully. More
importantly, at very mild conditions (30 ºC, 0.1 MPa CO2), a considerable turnover number (TON) value of 1800 was
obtained. The heterogeneous POPs catalyst can be easily recovered and reused for 10 times without loss of activity.
www.rsc.org/
O
Introduction
C
H2
cat.
OH
R
OH
+ CH3OH
O
O
O
+
CO2
Today in the 21st century, carbon dioxide (CO2), which was
mainly produced by the excessive burning of coal, petroleum
and natural gas, has become a big problem in climate change.1
On the other hand, CO2 is an abundant, renewable, nontoxic
and economical source of carbon and therefore a fascinating
C1 building block for fine chemicals’ synthesis. Considering
from a higher level, transformation of CO2 into value-added
chemicals assists the carbon cycle in nature, which is a crucial
goal in catalysis.2-7 In particular, the conversion of CO2 to cyclic
carbonates has attracted much attention due to the wide
applications of cyclic carbonates,8-11 such as polar aprotic
solvents, electrolytes in lithium-ion batteries and useful
intermediates for pharmaceuticals or other fine chemicals.
Recent research suggests that cyclic carbonates can be directly
hydrogenated to diols and methanol,12-14 and this reaction
might be a new practical pathway to produce methanol from
CO2 (Scheme 1).
cat.
R
R
Scheme 1 The conversion of CO2 to cyclic carbonates and
subsequent hydrogenation process.
efficiency (turnover frequency up to 46000 h-1).26 Kleij’s group
developed an aluminum complex based on an amino
triphenolate ligand scaffold, and this complex showed an initial
turnover frequency (TOF) up to 36000 h-1, which also
represents unprecedented high activity.27 North et al.
elucidated the synthesis of cyclic carbonates catalysed by
chromium and aluminium Salen complexes, more importantly,
these complexes displayed remarkable catalytic activity in the
synthesis of cyclic carbonates from a range of epoxide and
carbon oxide at ambient temperature and pressure.28,
29
Although these homogeneous catalytic systems displayed high
efficiency towards cyclic addition of CO2 to epoxides, their
difficult synthesis, complicated recycling problems as well as
the metal contamination of the products severely impede their
industrial applications.
Up to now, numerous catalytic systems have been
developed for the conversion of CO2 to cyclic carbonates. 15-25
In recent years, several homogeneous catalytic systems
displayed considerable high efficiency towards this
transformation. For example, Maeda and co-workers reported
metal porphyrin dimer and trimer platforms as catalysts for
the synthesis of cyclic carbonates, which obtained an ultrahigh
Therefore, the immobilization of these highly efficient
homogeneous catalysts has come up naturally in our mind.30
Until now, several immobilized (or heterogenized) catalytic
systems have been developed to realize the catalyst
recovering and reusing.31-33 For instance, as
a classical
a.School of Environment and Civil Engineering, Dongguan University of Technology,
Dongguan 523808, China
anchoring way, silica and polymer are the two most used
carrier to support homogeneous catalyst, however, in this
model, the active catalytic species are inhomogeneously
dispersed and pendant into the pore volume, which probably
b.Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian,116023, China.
Electronic Supplementary Information (ESI) available: NMR copies, ICP data, TGA
analysis and CO2 adsorption analysis. See DOI: 10.1039/x0xx00000x
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leads to pore blocking and finally deactivate the catalytic
process.34 In addition, the catalytic efficiency of these classical
immobilized catalysts, which was evaluated by TOF value, are
not satisfactory compared with their homogeneous
counterparts.
Experimental
General information
Carbon dioxide is commercially available with 99.99% purity.
All the solvents were purchased with analytically pure without
further purification, and epoxides were also purchased with
high purity (>98%). Vinyl functionalized porphyrin (vinyl-
porphyrin) was synthesized according to literature.50
In the past decade, porous organic polymers (POPs), which
were characterized for its high surface areas, hierarchical pore
structures and stable covalently linked bond, have emerged as
a versatile functional materials.35-42 And nowadays, POPs
materials were broadly applied in the field of catalysis,35-40 gas
sorption43, 44 and pollutant removal,45, 46 etc. As for catalysis,
heterogeneous POPs catalysts consist of isolated and well-
defined active sites that are spatially separated, which can also
be recognized as single-site catalysts.40 On the other hand,
because of the adsorption concentration effect that was
endowed by the high surface areas and hierarchical pore
structures of POPs materials, POPs catalyst generally exhibits a
far better catalytic activity than classical anchoring catalysts.47
In this contribution, we demonstrate a series of Mg-
porphyrin complex doped divinylbenzene (DVB) based POPs
catalyst through the method of free radical polymerization
under solvothermal conditions (Scheme 2).48-62 Through tuning
the molar ratio of Mg-porphyrin complex and DVB monomers,
five new doped POPs catalysts, which were designated as Mg-
NMR data were obtained on
a Bruker AV-400 MHz
spectrometer. GC analyses were performed on an Agilent
7890A equipped with a capillary column (HP-5, 30 m length,
0.32 mm diameter), using a flame ionization dector. Solid 13C
MAS NMR spectra were recorded on a VARIAN Infinity plus
spectrometer at a magic angle spinning rate of 6 kHz.
Nitrogen sorption isotherms of POPs catalysts at liquid
nitrogen temperature (77 K) were obtained on a Micromeritic
ASAP 2020M analyzer. The Brunauer–Emmett–Teller (BET)
method was utilized to calculate the specific surface areas and
the nonlocal density function theory (NLDFT) was applied for
the estimation of pore size, pore volume and pore distribution.
The range of P/P0 used for calculating the BET surface areas
are from 0.05-0.20. TGA curves were measured on a STA449F3
analyzer. Transmission electron microscopy (TEM) images
were obtained using a JEM-2100 with an accelerating voltage
of 200 kV. Scanning electron microscopy (SEM) was performed
using a JSM-7800F with an accelerating voltage of 0.01–30 kV.
Inductively coupled plasma spectroscopy (ICP) was tested on a
PerkinElmer apparatus Optima 7300 DV. The CO2 adsorption
isotherms of POPs catalysts at 273 K were carried out on IGA-
100A Hiden Analytical.
Por\DVB(1:20)@POPs,
Mg-Por\DVB(1:40)@POPs,
Mg-
Por\DVB(1:60)@POPs, Mg-Por\DVB(1:80)@POPs and Mg-
Por\DVB(1:100)@POPs, were systematically synthesized. And
their catalytic activities toward the coupling reaction of CO2
with epoxides were investigated, the effect of doping ratio
(Mg-porphyrin complex to DVB) towards catalytic efficiency
was also studied and discussed.
Preparation and characterization
Synthesis of vinyl-Mg-porphyrin monomer. A sample of 115
mg (0.16 mmol) of vinyl-porphyrin was dissolved in 10 mL
CH2Cl2 in a round-bottom flask. Then 0.5 mL (3.6 mmol) of
triethylamine was added followed by 413 mg (1.6 mmol) of
MgBr2·O(Et)2. The mixture was stirred for 20 minutes at room
temperature. Then the reaction finished, which can be
monitored by thin-layer chromatography. The finished
reaction mixture was diluted with another 30 mL of CH2Cl2,
washed with 10% NaHCO3 aqueous solution (2
☓ 30 mL), dried
with anhydrous Na2SO4 and the filtrate was concentrated to 5
mL. Finally, chromatography on alumina column with CH2Cl2
elution yielded residual vinyl-porphyrin. Elution with
CH2Cl2/aceton (1:1) afforded 107 mg vinyl-Mg-porphyrin (90%).
Representative synthetic procedure of POPs catalyst, taking
Mg-Por\DVB(1:20)@POPs as an example. Vinyl-Mg-porphyrin
complex (74 mg, 0.1 mmol), DVB (260 mg, 2 mmol) and
azodiisobutyronitrile (AIBN, 17 mg, 5 wt%) were dissolved in 5
mL of THF. The mixture was transferred into an autoclave and
maintained at 120 ºC under solvothermal conditions for 24 h.
When the polymerization was finished, after the autoclave was
cooled, the catalyst was took out in a swollen state, and the
photograph of the swollen state of the synthesized catalyst is
shown in Scheme 2. After evaporation of solvent, a purple
solid with quantitative yield was obtained and denoted as Mg-
Scheme 2 Preparation of Mg-Por\DVB(1:n)@POPs (n = 20, 40,
60, 80 and 100) via solvothermal synthesis.
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were recorded for all the five POPs materials, which indicated
the hierarchical pore structures (the coexistence of micropores
and mesopores) of these materials. Take Mg-
Por\DVB(1:20)@POPs as an example, based upon the NLDFT
calculations, the pore sizes of two types are distributed around
0.5-1.5 and 3-10 nm (Fig. S6), respectively. This developed
hierarchical pore structures are regarded to be very favourable
for the diffusion and mass transfer processes in catalysis. In
addition, the calculation results showed that, with the
decrease of doped proportion of Mg-porphyrin monomer
(from 1:20 to 1:100), the specific BET surface areas increased
from 708 to 2077 m2/g while the total pore volumes also
increased from 0.70 to 2.26 cm3/g (Table 1). These results
implied that an excessive doping of Mg-Porphyrin monomers is
not beneficial for the pore structures, and a relatively low
doping ratio (approximate 1:100) is best for the improving of
specific surface areas and total pore volumes. More
importantly, the high surface area (SBET = 2077 m2/g) and large
pore volume (2.26 cm3/g) of Mg-Por\DVB(1:100)@POPs
represents outstanding physical property parameters of POPs
material, which might attract significant attentions of researchers in
the area of porous organic polymers.
Por\DVB(1:20)@POPs. Other four POPs catalysts were
prepared similarly.
Catalytic studies
Reactions were performed in a 25 mL autoclave with vigorous
stirring. For a typical catalytic run, propylene oxide (9.28 g, 160
mmol), Mg-Por\DVB(1:20)@POPs catalyst (28 mg, equivalent
to 0.008 mmol Mg, substrate/Mg = 20000) and TBAB (52 mg)
were added into the autoclave without any solvent. After
sealing and purging with CO2 3 times, the autoclave was placed
under a constant pressure of CO2 which was controlled by a
pressure regulating valve, then heated to the required
temperature. After reaction, the autoclave was cooled to room
temperature and slowly depressurized, then 5 mL methanol
was added to dilute the mixture. The catalyst was recovered
by centrifugation, and the filtrate was analyzed by gas
chromatography (with an internal standard of n-butyl alcohol)
to determine the yield. Representative GC chromatography is
shown in Figure S4.
Results and discussion
Materials synthesis and characterization
As shown in Scheme 2, Mg-Por\DVB@POPs catalysts were
systematically afforded through the method of free radical
polymerization under solvothermal conditions. Solvothermal
synthetic technique is a similar process of hydrothermal
synthesis which is very common used in molecular sieve
synthesis. AIBN was used as a free radical initiator, and THF
was not only used as a solvent, but also played the role of
template for the formation of hierarchical pore structures. The
olefin polymerization, which is extensively applied in plastic
industry, is very efficient once triggered, provides almost
quantitative yields. So the solvothermal synthesis process is
very competent in the synthesis of porous organic polymers.
One might wonder why we didn’t synthesize Mg-
Porphyrin@POPs that was polymerized solely by Mg-porphyrin
complex, actually, we have attempted to prepare Mg-
Porphyrin@POPs. However, we found that vinyl-Mg-porphyrin
complex cannot be self-polymerized, which might be ascribed
to the low reactivity of this complex. Therefore, in this
situation, DVB was introduced as a powerful cross-linking
agent, and Mg-Por\DVB@POPs catalysts can be easily
synthesized through the method of solvothermal synthesis.
Five different POPs with different monomer ratios (Mg-
porphyrin complex to DVB equals to 1:20, 1:40, 1:60, 1:80 and
1:100) were systematically synthesized, and the effect of
doping ratio (Mg-porphyrin complex to DVB) towards catalytic
efficiency was studied and discussed hereinafter.
Table 1. BET surface areas and pore volumes of POPs materials
SBET
(m2/g)
708
758
839
Total pore
volumes (cm3/g)
Materials
Mg-Por\DVB(1:20)@POPs
Mg-Por\DVB(1:40)@POPs
Mg-Por\DVB(1:60)@POPs
Mg-Por\DVB(1:80)@POPs
Mg-Por\DVB(1:100)@POPs
0.70
0.71
0.75
0.82
2.26
886
2077
Representative SEM (Fig. 1A) and TEM (Fig. 1B) images of
Mg-Por\DVB(1:20)@POPs further confirm the rough surfaces
and the existence of hierarchical porosities. As shown in Fig.
1A and Fig. 1B, beautiful hierarchical porosities of varying sizes
interlaced, and this porous structural property is very
beneficial for the diffusion of products and reactants,
especially for gas-involved conversions. Elemental distribution
in catalyst Mg-Por\DVB(1:20)@POPs was determined by the
energy-dispersive X-ray spectroscopy (EDX) mapping technique
in scanning electron microscopy (Fig. 2). Moreover, the highly
dispersed character of all functional elements (Mg, N, and C)
validates the homogeneously distributed active functional
sites. This kind of doping in hierarchical pore environments
creates spatially separated active sites for the catalytic CO2
transformation process which will be discussed later.
The representative Mg-Por\DVB(1:20)@POPs is stable in an
air atmosphere, and its chemical structure and composition
was defined by solid-state 13C and ICP analysis. The peaks
ranging from 120 to 150 ppm (Figure 3) are attributed to the
aromatic carbons of Mg-Por\DVB(1:20)@POPs, the peak at
around 40 ppm is assignable to the CH2 group directly linked to
the aromatic ring, and the peak at around 26 ppm is assignable
to the “−CH2CH2−” linker. ICP test shows the real Mg content
The information of pore structures and specific surface
areas of the five synthesized Mg-Porphyrin@POPs were
systematically investigated through nitrogen adsorption and
desorption experiments at 77 K. As shown in Fig. S5, the curves
of five POPs materials all displayed combined features of type I
and type IV. It is worth noting that obvious hysteresis loops
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of Mg-Por\DVB(1:20)@POPs is 0.70 wt% while the calculated
value is 0.77 wt% based on elemental analysis, which is
consistent to the theoretic value of 0.73%. For the ICP data of
other POPs materials, please see Table S1.
benzene ring
“−CH2CH2−” linker
porphyrin
skeleton
benzene ring
“−CH2CH2−” linker
Fig.
Por\DVB(1:20)@POPs
3
Solid-state 13C NMR spectrum of Mg-
Evaluation of Catalytic Performance
First, the catalytic activities of five Mg-Por\DVB@POPs
materials that with different Mg-Porphyrin doping ratios (from
1:20 to 1:100) were assessed for the cycloaddition reaction of
CO2 and propylene oxide (Table 2). With the co-catalyst of
tetrabutylammonium bromide (TBAB, which plays the role of a
nucleophile), the order of the activity of POPs materials with
different Mg-Porphyrin doping ratios was found to be Mg-
Por\DVB(1:20)@POPs
Por\DVB(1:60)@POPs
>
>
Mg-Por\DVB(1:40)@POPs
Mg-Por\DVB(1:80)@POPs
>
>
Mg-
Mg-
Por\DVB(1:100)@POPs (entries 1-5, Table 2), the TOF value
decreased from 11600 to 7000 h-1 and this order might be
explained as the negative embedding effect of the low doping
ratios. When the doping ratio of Mg-Porphyrin\DVB was 1:20,
the active Mg sites were appropriately exposed on the
accessible surface of POPs material, and a high TOF value of
11600 h-1 was obtained (entry 1, Table 2); with the decrease of
doping ratio (from 1:20 to 1:100), the accessible Mg sites also
decreased due to the negative embedding effect; however, a
TOF value of 7000 h-1 was still obtained with the low doping
ratio material Mg-Por\DVB(1:100)@POPs (entry 5, Table 2).
When the homogeneous vinyl-Mg-porphyrin analogue was
used as the catalyst, a high TOF value of 10800 h-1 was
obtained (entry 6, Table 2), which is slight lower compare to
the heterogeneous Mg-Por\DVB(1:20)@POPs catalyst. The
control catalyst of Mg-Por\DVB(1:20)@POPs without TBAB
was also investigated, and only trace product was detected
(entry 7, Table 2), which indicated the co-catalyst (the
nucleophile of TBAB) is essential for the catalysis process.
When the nucleophile of TBAB was used only (without Mg-
Por\DVB@POPs) for this reaction, only 8% yield was obtained
(entry 8, Table 2), which implied the necessity of Mg-
Por\DVB@POPs materials that acted as the heterogeneous
Lewis acid catalysts. Under these reaction conditions, without
catalysts, no product was detected (entry 9, Table 2). We have
also increased the catalyst amount (substrate/catalyst = 10000
compared to the original S/C = 20000), and the yield was
increased to 83%, the TOF value is 8300 in this situation (entry
10, Table 2).
Fig.
1 (A) SEM image and (B) TEM image of Mg-
Por\DVB(1:20)@POPs
Fig.
2 Elemental distribution in Mg-Por\DVB(1:20)@POPs
determined by SEM-EDX: (A) magnesium, (B) nitrogen, (C)
carbon, and (D) original image.
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Table 2. Catalytic activities of various catalysts in the pressure was reduced to atmosphere pressure (0.1 MPa), a
cycloaddition reactions of CO2 and propylene oxidea
TON value of 2600 was still obtained at 40 (entry 2, Table 3).
When the temperature was reduced to 30 , a temperature
℃
℃
which was easily reached in summer, high TON values of 2400
and 1800 were still obtained at 1 MPa and 0.1 MPa,
respectively. To obtain a relative high yield, we have increased
the catalyst amount (substrate/catalyst = 1000 compared to
the original S/C = 20000, entry 5, Table 3); a yield of 82% was
obtained at 40 °C for 48 h, the TON value is 820 while the TOF
value is 17.1 h-1. These researches clearly indicate that Mg-
Por\DVB@POPs could be a real CO2 alleviating and energy-
saving catalyst.
Entry
Catalyst
Yield
(%)
58
TOF
(h-1)
Mg-Por\DVB(1:20)@POPs
Mg-Por\DVB(1:40)@POPs
Mg-Por\DVB(1:60)@POPs
Mg-Por\DVB(1:80)@POPs
Mg-Por\DVB(1:100)@POPs
vinyl-Mg-porphyrin
1
2
11600
10600
9800
8400
7000
10800
―
53
3
49
4
42
5
35
6
54
without TBAB
7
trace
8
TBAB only
8
―
No catalyst
Mg-Por\DVB(1:20)@POPsb
aReaction conditions: propylene oxide (13.0 g, 224 mmol),
9
N.R.
―
10
83
8300
TBAB (50 mg), an initial pressure of
3
MPa,
substrate/catalyst = 20000 (catalyst amount equal to the
amount of Mg sites), 120 °C, 1 h. The selectivities of all
results are >99%. bsubstrate/catalyst = 10000. All the results
are averaged by two runs.
Table 3. Catalytic activities of Mg-Por\DVB(1:20)@POPs in
conversion of CO2 to cyclic carbonates at 40 and 30 °Ca
Fig. 4 Recyclability test of Mg-Por\DVB(1:20)@POPs. Reaction
conditions: propylene oxide (13.0 g, 224 mmol), TBAB (50 mg),
an initial pressure of 3 MPa, substrate/catalyst = 20000
(catalyst amount equal to the amount of Mg sites), 120 °C, 1 h.
The selectivities of all results are >99%.
Entry Temperature Pressure
Yield
(%)
16
TON
TOF
(h-1)
(°C)
40
40
30
30
40
(MPa)
1
1
2
3200 66.7
2600 54.2
0.1
1
13
3
12
2400
1800 37.5
820 17.1
50
4
5b
0.1
9
1
82
aReaction conditions: propylene oxide (13.0 g, 224 mmol),
TBAB (50 mg), substrate/catalyst = 20000 (catalyst amount
equal to the amount of Mg sites), 48 h. bsubstrate/catalyst =
1000. The selectivities of all results are >99%. All the results
are averaged by two runs.
Although our heterogeneous POPs catalysts show high
efficiency in catalytic synthesis of cyclic carbonates from CO2,
it is very appealing to covert CO2 at very mild temperatures
with heat energy from the neighbouring environment to avoid
the production of extra CO2. Regrettably, so far, few promising
results have been reported. In 2013, Deng’s group reported a
Fig. 5 Reaction conditions: substrate (22.4 mmol), TBAB (10
mg), an initial pressure of 3 MPa, Mg-Por\DVB(1:20)@POPs
(3.8 mg, substrate/catalyst = 20000, catalyst amount equal to
the amount of Mg sites), 120 °C, 5 h. The selectivities of all
results are > 99%.
relatively high efficient POP catalyst concerning this reaction,
63
In addition, the catalyst of Mg-Por\DVB(1:20)@POPs could
be easily recycled by simple filtration or centrifugation
because of its insolubility property in almost all solvents. The
recovered POPs catalyst showed nearly the same reactivity as
the original, and the catalyst Mg-Por\DVB(1:20)@POPs can be
and a TON value around 200 was obtained at 25
℃
research, our selected POPs catalyst Mg-Por\DVB(1:20)@POPs
.
In this
was tested at 40 and 30 ℃, respectively. As shown in entry 1
of Table 3, a high TON result of 3200 (TOF = 66.7 h-1) was
achieved at 40 ℃ and 1 MPa pressure of CO2. When the CO2
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9
C. Martín, G. Fiorani and A. W. Kleij, ACS Catal., 2015, 5,
1353-1370.
simply recycled and reused at least five times by simple
filtration (Fig. 4). Moreover, as shown in Fig. 5, the versatility
of Mg-Por\DVB(1:20)@POPs was further studied. Under the
similar reaction conditions as listed in Table 2, and the reaction
time was prolonged to 5 hours, satisfied yields of the
corresponding cyclic carbonates were obtained.
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Conclusions
By adjusting the polymer monomer ratio, five different Mg-
porphyrin complex doped DVB-based POPs catalysts (Mg-
Por\DVB@POPs) were systematically afforded through the
method of free radical polymerization under solvothermal
Poater, S. Wannakao, L. Cavallo and V. D’Elia, ACS
Sustainable Chem. Eng., 2017, 5, 6392-6397.
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porphyrin monomer (from 1:20 to 1:100), the specific BET
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pore volumes also increased from 0.70 to 2.26 cm3/g. These
data trends may have a positive inspiration and guidance for
6
the researchers in the field of porous organic polymers. The 20 X.-H. Ji, N.-N. Zhu, J.-G. Ma and P. Cheng, Dalton Trans.,
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order of the activity of POPs materials with different Mg-
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Por\DVB(1:20)@POPs
Por\DVB(1:60)@POPs
>
>
Mg-Por\DVB(1:40)@POPs
Mg-Por\DVB(1:80)@POPs
>
>
Mg-
Mg-
Por\DVB(1:100)@POPs concerning the catalytic cycloaddition
of propylene oxide and CO2, and this activity data trend was
attributed to the negative embedding effect of the active Mg
sites. Interestingly, there was no obvious relationship between
the catalytic activities and the parameters of specific areas and
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embedding effect that caused by the large proportion of DVB
in POPs materials played a major role in affecting the activity.
A high TOF value of 11600 h-1 was obtained by using Mg-
Por\DVB(1:20)@POPs catalyst under the condition of 120 ℃
and 3 MPa. Under ambient condition (30 and 0.1 MPa), a
℃
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PAPER
Graphic Abstract
Mg-Porphyrin complex doped divinylbenzene based POPs were afforded as heterogeneous catalysts for the conversion of CO2 to
cyclic carbonates.
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