Porous Organic Polymers Constructed from Tr?ger's Base as Efficient Carbon Dioxide Adsorbents and Heterogeneous Catalysts

Article abstract of DOI:10.1002/cctc.201701534

Through a radical solvothermal polymerization method, we synthesized two porous organic polymers based on Tr?ger's base (POP-TB and POP-Me-TB) from the corresponding vinyl-functionalized monomers (2,8-divinyl-6H,12H-5,11-methanodibenzo[b,f]diazocine and 2

Full text of DOI:10.1002/cctc.201701534

DOI: 10.1002/cctc.201701534
Full Papers
Porous Organic Polymers Constructed from Trçger’s Base
as Efficient Carbon Dioxide Adsorbents and
Heterogeneous Catalysts
+
[a, b]
+ [a]
[a]
[c]
[a]
[c]
Zhifeng Dai ,
Yongquan Tang , Qi Sun, Xiaolong Liu, Xiangju Meng,* Feng Deng,
[a]
and Feng-Shou Xiao*
Through a radical solvothermal polymerization method, we
synthesized two porous organic polymers based on Trçger’s
base (POP-TB and POP-Me-TB) from the corresponding vinyl-
functionalized monomers (2,8-divinyl-6H,12H-5,11-methanodi-
benzo[b,f]diazocine and 2,8-divinyl-4,10-dimethly-6H,12H-5,11-
ethanodibenzo[b,f]diazocine; v-TB and v-Me-TB). The structure
and porosity of these polymers are verified by using solid-state
isotherms, and CO sorption tests. They exhibit high surface
2
areas and moderate pore volumes, which give high CO ad-
2
À1
sorption capacities (90 and 71 mg
g
at 273 K and 60 and
CO2
À1
44 mgCO2
g
at 298 K for POP-TB and POP-Me-TB, respectively)
under a CO pressure of 1 bar. In addition, they display excel-
2
lent catalytic activities together with highly stability as hetero-
geneous catalysts in the benchmark Knoevenagel reactions.
NMR spectroscopy, elemental analysis, SEM, TEM, N sorption
2
Introduction
[
9–12]
Homogeneous organocatalysts have been used widely in or-
ganic synthesis and pharmaceutical chemistry because of their
nagel, Michael, and transesterification reactions.
Trçger’s
base (TB) was first reported by Julius Trçger in 1887, and the
recent development of TB-based solid base catalysts has at-
tracted attention because of its interesting stereochemistry,
[
1]
unique activity and selectivity. However, the relatively compli-
cated recycling of these organocatalysts is a challenge for their
[
2]
[13]
industrial application. The solution for this issue is to support
supramolecular chemistry, and strong base properties. Wang
[
2f,3]
[4]
[14]
the organocatalysts on zeolites,
carbons, magnetic nano-
and co-workers used the Sonogashira–Hagihara coupling re-
[
2i,5]
[6]
particles,
and metal–organic materials (MOFs). In these
action to prepare a TB-functionalized organic nanoporous
polymer, which showed an excellent activity in the addition of
diethylzinc to 4-chlorobenzaldehyde as a heterogeneous cata-
cases, the relatively low concentration and easy leaching of or-
ganocatalysts influence their applications strongly. To over-
come these problems, the preparation of porous organocata-
[15]
lyst. Later, Corma et al. showed that the TB active sites in
SBA-15 exhibit excellent catalytic activities in Knoevenagel re-
actions, the S-arylation of aryl halides, and azide–alkyne cyclo-
addition, although the TB concentration in these catalysts was
relatively low. Besides this progress, a series of materials has
[
6d,7,8]
lysts has been suggested.
Among organocatalysts, base catalysts such as amines
have been applied widely in organic reactions such as Knoeve-
[9]
[16]
+
+
been functionalized with TB for CO capture and conversion.
2
[
a] Dr. Z. Dai, Y. Tang, Dr. Q. Sun, Prof. X. Meng, Prof. F.-S. Xiao
Key Laboratory of Applied Chemistry of Zhejiang Province and
Department of Chemistry
Porous organic polymers (POPs), which have stable covalent
bonds and always possess an excellent stability, large pore
volume, high surface area, and designable structure, are an
Zhejiang University
Hangzhou, Zhejiang, 310028 (P.R. China)
E-mail: mengxj@zju.edu.cn
[17]
emerging class of porous materials. Recently, our group has
reported a series of porous organic ligands (POLs) synthesized
through solvothermal radical polymerization methods from the
corresponding vinyl-functionalized ligand monomers them-
selves, for which the concentration of organic ligands was
maximized because of the composition of the porous polymers
with pure organic ligands. For example, if we used vinyl-func-
tionalized diphosphine monomers (v-dppe), a POP called POL-
fsxiao@zju.edu.cn
+
[b] Dr. Z. Dai
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,
School of Chemistry
Sun Yat-Sen University
Guangzhou 510275 (P.R. China)
[c] Dr. X. Liu, Prof. F. Deng
State Key Laboratory of Magnetic Resonance and
Atomic and Molecular Physics
Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences,
Wuhan 430071(P.R. China)
[12b]
dppe was synthesized.
As a result of the high ligand con-
centration, the supported Rh catalyst shows extraordinary cata-
lytic properties in the heterogeneous hydroformylation of ole-
fins. In particular, the catalytic activity and selectivity of these
heterogeneous catalysts even outperform those of their homo-
geneous counterparts.
+
[
] These authors contributed equally to this work.
Supporting information for this article can be found under:
https://doi.org/10.1002/cctc.201701534.
This manuscript is part of a Special Issue on “Supported Molecular
Catalysts”.
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The solid base materials are potentially important for gas
sorption, separation, and catalysis and it is interesting to devel-
op stable and porous solid base materials. In this work, we syn-
thesized two TB-derived porous organic polymers (POP-TB and
POP-Me-TB) from a simple radical polymerization of the corre-
sponding vinyl-functionalized TB monomers (v-TB and v-Me-
TB) under solvothermal conditions. In particular, the POPs were
obtained quantitatively, and the TB ligands were retained fully
in the frameworks. The combination of the basic properties of
TB and the high concentration of the ligands in the framework
offer a good opportunity to obtain solid base materials for gas
sorption (CO ) and base-catalyzed reactions. CO sorption tests
2
2
indicate that these porous polymers have a high CO capture
2
À1
capacity (90 and 71 mg
g
of CO2 at 273 K and 60 and
CO2
À1
44 mgCO2
g
at 298 K for POP-TB and POP-Me-TB, respectively).
Knoevenagel tests show that these porous polymers are highly
efficient catalysts with both high activities and excellent stabili-
ties.
1
3
2
Figure 1. A) C MAS NMR spectrum, B) N sorption isotherm, C) SEM image,
and D) TEM image of POP-TB.
64.4 ppm are attributed to the methylene carbon atom linked
Results and Discussion
to the N atoms, whereas the peaks at d=127.8–146.4 ppm are
related to the aryl backbones. Similarly, POP-Me-TB exhibits
almost the same spectrum (Figure S1). Elemental analysis of
the polymers shows that the compositions of POP-TB (C
To demonstrate the “proof-of-concept”, we first prepared the
vinyl-functionalized TB monomers 2,8-divinyl-6H,12H-5,11-
methanodibenzo[b,f]diazocine (v-TB) and 2,8-divinyl-4,10-di-
7
7
4.7%, N 9.7%, H 6.8%) and POP-Me-TB (C 80.4%, N 9.3%, H
.3%) are consistent with the molecular structures of the mon-
methyl-6H,12H-5,11-ethanodibenzo[b,f]diazocine
(v-Me-TB;
Schemes S1 and S2). After radical solvothermal polymerization,
two TB-based POPs (POP-TB and POP-Me-TB) were obtained in
quantitative yields (Scheme 1). Notably, the radical solvother-
mal synthesis of POPs is facile and efficient compared with
omers v-TB and v-Me-TB, which indicates that the structure of
TB in POP-TB and POP-Me-TB remained after solvothermal
polymerization. Further experiments show that these polymers
are insoluble in most organic solvents, which include DMF,
THF, toluene, and DMSO.
[17]
metal-catalyzed cross-coupling reactions and self-assembly.
The synthesis of the TB-functionalized polymers was verified
13
The porosity of the polymers was investigated by measuring
by using C magic-angle spinning (MAS) NMR spectroscopy,
13
the N sorption isotherms at 77 K. The N sorption isotherms of
2 2
elemental analysis, SEM, and TEM. The C solid-state NMR
spectrum of POP-TB is shown in Figure 1A. Compared with the
spectrum of the v-TB monomer, the disappearance of the
peaks at d=110–120 ppm that correspond to the vinyl bonds
and the simultaneous appearance of two new peaks at d=
POP-TB are shown in Figure 1B. The deep step at a low relative
pressure (P/P <0.1) reveals the presence of the microporosity
0
in the polymer framework. The hysteresis loop at P/P =0.4–0.7
0
suggests the presence of a mesoporous structure in the
sample. The pore size distribution of POP-TB calculated by
using nonlocal density function theory (NLDFT) was mainly
28.0 and 40.9 ppm assigned to alkyl carbon atoms indicate
that the polymerization of the double bonds is complete in
0
.5–3 and 2.6–30 nm (Figure S2). The BET surface area and
the spectrum of POP-TB. The overlapped peaks at d=46.5 and
2
À1
pore volume of POP-TB are estimated at 568 m g and
3
À1
0.49 cm g , respectively. The N sorption isotherms of POP-
2
Me-TB (Figure S3A) indicate a hierarchical porous polymer,
2
À1
which has a high BET surface area (575 m g ) and large pore
3
À1
volume (0.36 cm g ). The pore size distribution of POP-Me-TB
is mainly at 1.8 and 4.1 nm (Figure S3B).
Thermogravimetric analysis (TGA; Figure S4) indicates that
the decomposition temperature of POP-TB and POP-Me-TB
under N is approximately 643 K, which reflects their high ther-
2
mal stability. We used SEM and TEM to further confirm the
presence of large mesopores (Figure 1C and D and Figure S5).
Solid base materials have attracted much attention because
of their excellent adsorption capacity for acidic CO and might
2
be good candidates to replace methods based on amine solu-
tion wet scrubbing used widely in industry. As a result of the
basic properties of TB (pK (N)=1.15) and the resulting CO -
HB
2
Scheme 1. Proposed structure of POP-TB.
philicity of the materials, we propose that POP-TB and POP-
&
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[
a]
Table 1. Catalytic performance of POP-TB in the Knoevenagel reaction.
[
b]
Entry
1
Catalyst
Catalyst ratio [%]
T [K]
Conversion [%]
POP-TB
TB
–
POP-TB
POP-TB
POP-Me-TB
POP-TB
1.7
1.7
0
0.5
1.7
1.7
1.7
313
313
313
313
300
313
313
96.5
99.0
19.6
86.1
84.9
74.0
91.8
[
c]
2
3
4
5
6
7
[
d]
[
a] Reaction conditions: 10 mmol benzaldehyde, 10 mmol malononitrile,
catalyst, solvent-free condition at 313 K for 3 h. [b] Determined by using
GC. [c] Homogeneous catalyst TB was used. [d] Recycled for 4 times.
2
Figure 2. CO sorption isotherms of POP-TB and POP-Me-TB.
In addition, the higher CO uptake capacity of the catalyst is
2
more favorable to obtain higher catalytic activity. This phe-
Me-TB should have a high CO uptake. Thus, we tested the
nomenon might be related to the higher CO uptake capacity
2
2
CO2 sorption capacity of POP-TB and POP-Me-TB. At 273 K,
of the POP-TB, which has a relatively larger pore volume and
pore size that plays an important role in the catalytic activity
in Knoevenagel reactions.
À1
POP-TB and POP-Me-TB can absorb 90 and 71 mgCO2
g
of CO2
at a pressure up to 1 bar of pure CO , and the uptake is re-
2
À1
duced to 60 and 44 mgCO2 g , respectively, if the temperature
The recyclability of the POP-TB catalyst is shown in Figure 3.
Notably, after simple centrifugation and washing with EtOAc
under ultrasound, POP-TB could be reused readily four times
without a significant decrease in the activity (91.8%; Table 1,
entry 7), which indicates the robustness of the POP. Further-
more, we tested the substrate scope of the aldehyde in the
Knoevenagel reaction over heterogeneous POP-TB and POP-
Me-TB and homogeneous TB. If the substrates possess elec-
tron-donating or -withdrawing groups such as p-methylbenzal-
dehyde and 4-bromobenzaldehyde, the reactions could be fin-
ished in 3 h with quantitative yields (Table 2, entries 1 and 2)
over the three catalysts. Impressively, POP-TB is compatible
with long-chain alkylaldehydes, which include phenylpropyl al-
dehyde and octanal, to reach a conversion of 90.5 and 88.0%,
respectively (Table 2, entries 3 and 4). These catalytic activities
are superior to those of homogeneous TB (83.5 and 85.7%;
is increased to 298 K (Figure 2). These values are comparable
[
17c,18]
to those reported previously (Table S1).
The relatively
higher adsorption capacity of POP-TB than that of POP-Me-TB
is reasonably attributed to the higher pore volume of POP-TB
3
À1
3
À1
(
0.49 cm g ) than that of POP-Me-TB (0.36 cm g ), as demon-
strated by the N sorption isotherm. The isosteric heat of CO2
2
adsorption (Qst) for POP-TB and POP-Me-TB is 25.8 and
À1
2
4.8 kJmol , respectively, calculated from the Clausius–Cla-
peyron equation. The relatively low Qst values of POP-TB and
POP-Me-TB are favorable for the desorption of CO from the
2
polymers with a low energy penalty.
To investigate the heterogeneous catalytic properties, Knoe-
venagel reactions were chosen as a benchmark reaction. At
313 K and under solvent-free reaction conditions, POP-TB
could catalyze the condensation reaction of benzaldehyde and
malononitrile efficiently with the conversion of the benzalde-
hyde at 96.5% (Table 1, entry 1), which is comparable to that
of the homogeneous catalyst TB of 99.0% (Table 1, entry 2). If
the catalyst was removed from the reaction system, the con-
version of the reaction is relatively low (19.6%; Table 1,
entry 3). If the catalyst loading was reduced from 1.7 to
0.5 mol%, an increase of the reaction time from 3 to 5 h is re-
quired to achieve a conversion of 86.1% (Table 1, entry 4). We
also tested the catalytic activity of POP-TB at room tempera-
ture (300 K). Under the typical conditions, the heterogeneous
catalyst POP-TB could be used to obtain a conversion of 84.9%
in 5 h (Table 1, entry 5), which is comparable to that of TB im-
[
15b]
mobilized on mesoporous SBA-15.
The catalytic properties
of POP-Me-TB were also tested under similar conditions and
can be used to obtain a conversion of 74.0% (Table 1, entry 6)
under the same reaction conditions. The lower activity of POP-
Me-TB than POP-TB may be attributed to their different charac-
teristics, as indicated by the N sorption isotherms.
Figure 3. Recycling test in the Knoevenagel reaction over POP-TB.
2
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polymerization from the corresponding vinyl-functionalized
monomers. As a result of the high surface area and moderate
porosity of the structures, the porous organic polymers show
Table 2. Catalytic performance of POP-TB in the Knoevenagel reaction
with various substrates.
[
a]
high CO adsorption capacity and excellent catalytic properties
2
in the Knoevenagel reaction as heterogeneous catalysts.
[
b]
Entry
1
Substrate
Catalyst
Conversion [%]
Experimental Section
POP-TB
POP-Me-TB
TB
POP-TB
POP-Me-TB
TB
POP-TB
POP-Me-TB
TB
POP-TB
POP-Me-TB
TB
POP-TB
POP-Me-TB
TB
POP-TB
POP-Me-TB
TB
POP-TB
POP-Me-TB
TB
98.5
99.0
99.0
99.0
99.0
99.0
90.5
56.4
83.5
88.0
68.3
85.7
51.4
28.8
99.0
54.1
62.7
87.0
53.5
7.5
General
Solvents were purified according to standard laboratory methods.
Other commercially available reagents were purchased in high
purity and used without further purification.
2
3
4
5
6
7
Synthesis of POP-TB
Typically, v-TB (1 g) was dissolved in DMF (10 mL), and azobisisobu-
tyronitrile (AIBN; 50 mg) was added. The mixture was transferred
into an autoclave and heated at 1008C for 24 h. After washing
with EtOAc and drying under vacuum, a white solid was obtained,
which was denoted as POP-TB.
Synthesis of POP-Me-TB
Typically, v-Me-TB (1 g) was dissolved in DMF (10 mL), and AIBN
87.5
(50 mg) was added. The mixture was transferred into an autoclave
and heated at 1008C for 24 h. After washing with EtOAc and
drying under vacuum, a white solid was obtained, which was de-
noted as POP-Me-TB.
[
a] Reaction conditions: 10 mmol aldehyde, 10 mmol malononitrile, 1.7%
mol POP-TB catalyst, solvent-free conditions at 408C for 3 h. [b] Deter-
mined by using GC.
Table 2, entries 3 and 4). However, if cinnamaldehyde, which
has a rotation-prohibiting double bond in the a position, was
employed the conversion decreased to approximately 51.4%
Catalytic tests
Typically, the catalyst was added to a 25 mL Schlenk tube
equipped with benzaldehyde (10 mmol) and malononitrile
(10 mmol). After stirring at 408C for 3 h under solvent-free condi-
tions, EtOAc was added, and the catalyst was removed by centrifu-
gation. The reaction conversion was determined by using GC. For
the recycling test, the catalyst was washed thoroughly with EtOAc
with ultrasonication, dried in air, and used directly for the next run.
(Table 2, entry 5), which is much lower than that of TB (99.0%;
Table 2, entry 5). This might be because the hindered rotation
of the double bonds could increase the steric hindrance of cin-
namaldehyde, which would reduce the catalytic activity for
condensation. In addition, this conversion is almost the same
as that of substrates with stronger steric effects, which include
isobutyraldehyde (54.1%; Table 2, entry 6) and 2-phenylpropio-
naldehyde (53.5%; Table 2, entry 7), whereas homogeneous TB
maintains almost the same activity (87.0 and 87.5%, respec-
tively; Table 2, entries 6 and 7). If these substrates are reacted
over POP-Me-TB, which has a relatively small pore volume,
much lower conversions were observed (Table 2, entries 3–7)
except for isobutyraldehyde. Possibly, if the relatively small iso-
butyraldehyde substrate is employed, the stronger basicity of
POP-Me-TB than POP-TB would dominate in the condensation
reaction rather than the pore volume. In this case, POP-Me-TB
shows a slightly higher conversion with isobutyraldehyde than
POP-TB. These results indicate that the heterogeneous POP-TB
and POP-Me-TB catalysts promote substrate adaptation and
size selectivity in Knoevenagel reactions.
Characterization
N sorption isotherms at 77 K were measured by using Micromerit-
2
ics ASAP 2020M and Tristar systems. The samples were outgassed
for 10 h at 1008C before the measurements. SEM was performed
by using a Hitachi SU 1510 and SU 4800. TEM was performed by
using a Hitachi HT-7700. TGA was performed by using a SDT Q600
V8.2 Build100 thermogravimetric analyzer under N2 flow. H NMR
spectra were recorded by using a Bruker Avance-400 (400 MHz)
spectrometer. Chemical shifts are expressed in ppm downfield
1
1
3
from Si(CH3)4 at d=0 ppm, and J values are given in Hz.
C
(100.5 MHz) cross-polarization magic-angle spinning (CP-MAS) NMR
spectra were recorded by using a Varian infinity plus 400 spectrom-
eter equipped with a MAS probe in a 4 mm ZrO rotor.
2
Acknowledgements
Conclusions
This work was supported by National Key Research and Develop-
ment Program of China (2017YFC0211101), National Natural Sci-
ence Foundation of China (21422306, 21720102001 and
We have synthesized two porous organic polymers based on
Trçger’s base (POP-TB and POP-Me-TB) by radical solvothermal
&
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Conflict of interest
The authors declare no conflict of interest.
Keywords: heterogeneous catalysis · mesoporous materials ·
organocatalysts · polymers · radical reactions
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Version of record online: && &&, 0000
ChemCatChem 2018, 10, 1 – 6
www.chemcatchem.org
5
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

FULL PAPERS
Z. Dai, Y. Tang, Q. Sun, X. Liu, X. Meng,*
F. Deng, F.-S. Xiao*
Basic instinct: Porous organic polymers
constructed from Trçger’s base are
highly efficient for CO capture and
2
&& – &&
Knoevenagel reactions.
Porous Organic Polymers Constructed
from Trçger’s Base as Efficient Carbon
Dioxide Adsorbents and
Heterogeneous Catalysts
&
ChemCatChem 2018, 10, 1 – 6
www.chemcatchem.org
6
ꢀ 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!