Synthesis and characterization of pyrrole-containing microporous polymeric networks

Article abstract of DOI:10.1016/j.polymer.2013.04.038

Two types of microporous polymeric networks have been prepared from monomers containing N-tert-butoxycarbonyl-protected pyrrole by FeCl ₃-mediated oxidative coupling polymerization. These materials were predominantly microporous (with BET surface areas of 828 m² g ^-1 and 1408 m² g^-1), exhibiting high CO ₂ uptake capacities (1.96 mmol g^-1 and 2.69 mmol g ^-1 at 273 K, 1 bar). Novel microporous polymeric films (with BET surface areas of 570 m² g^-1 and 593 m² g ^-1) were fabricated through in situ polymerization of monomers on a flat glass dish using a sol-gel process catalyzed by trifluoroacetic acid.

Full text of DOI:10.1016/j.polymer.2013.04.038

Polymer 54 (2013) 3254e3260
Contents lists available at SciVerse ScienceDirect
Polymer
journal homepage: www.elsevier.com/locate/polymer
Synthesis and characterization of pyrrole-containing microporous
polymeric networks
,
,
Yanqin Yang a b, Qiang Zhang a, Jifu Zheng a, Suobo Zhang a
*
a Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b University of Chinese Academy of Sciences, Beijing 100049, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Two types of microporous polymeric networks have been prepared from monomers containing N-tert-
Received 25 January 2013
Received in revised form
2 April 2013
Accepted 17 April 2013
Available online 24 April 2013
butoxycarbonyl-protected pyrrole by FeCl3-mediated oxidative coupling polymerization. These materials
were predominantly microporous (with BET surface areas of 828 m2 gꢀ1 and 1408 m2 ꢀ1), exhibiting
g
high CO2 uptake capacities (1.96 mmol gꢀ1 and 2.69 mmol gꢀ1 at 273 K, 1 bar). Novel microporous
polymeric films (with BET surface areas of 570 m2 gꢀ1 and 593 m2 ꢀ1) were fabricated through in situ
g
polymerization of monomers on a flat glass dish using a solegel process catalyzed by trifluoroacetic acid.
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
Microporous polypyrroles
Solegel process
Microporous film
1. Introduction
The incorporation of nitrogen-containing structures makes the
network electron-rich, resulting in the materials possessing high
A diverse range of microporous organic polymers (MOPs) with
simple chemical routes for their synthesis and high intrinsic levels
of porosity have recently spurred scientific interest in this class of
materials. Depending on their design and properties, MOPs have
been classified into covalent organic frameworks (COFs) [1e3],
hyper-crosslinked polymers (HCPs) [4,5], polymers with intrinsic
microporosity (PIMs) [6e8], conjugated microporous polymers
(CMPs) [9,10], and porous aromatic frameworks (PAFs) [11,12]. They
possess small pores (<2 nm) and very high surface areas and have
been found to have potential applications particularly in molecular
separations [13,14], heterogeneous catalysis [15,16], and gas storage
[17,18]. MOPs possessing functional units have also been reported
which fulfill certain tasks based on their functionalities [19e23].
Recently, some MOPs containing aromatic heterocyclic units have
been synthesized by FeCl3-mediated oxidative coupling polymeri-
zation [22,23]. For instance, Thomas and coworkers have synthe-
sized MOPs based on the poly(thienylene arylene) motif via
oxidative coupling polymerization promoted by FeCl3 [22a]. The
high density of thiophene functionalities in the networks makes
the materials good candidates for encapsulation of metal catalyst.
Han and coworkers have prepared a MOP named CPOP-1 via the
oxidative polymerization of 1,3,5-tri(9-carbazolyl)-benzene [23].
CO2 uptake capacity. Additionally, FeCl3-mediated oxidative poly-
merization exhibits cost-effective advantages such as cheap cata-
lyst, high yield, and room temperature reaction conditions which
are essential for the large scale production of porous materials
[22,23].
Polypyrrole as a conducting polymer has attracted considerable
attention due to its excellent properties, such as appreciable envi-
ronmental stability, biocompatibility, good optical and electrical
properties and relatively low production cost [24e26]. Micropo-
rous polypyrrole is of particular interest since it possesses a con-
jugated backbone with NeH functional groups. Porosity is typically
imparted to polypyrrole via a template process utilizing nano-
porous carbons as porogen [27e29].
The porous structure may have an effect on some properties of
electrode materials, such as mutual permeation with another
substance at the interface, mobility and separation of charge, per-
formance of sensor and so on [22a]. It has been reported that car-
bon nanotube and polypyrrole nanoporous composites are suited
to energy storage applications such as supercapacitors and sec-
ondary batteries [29]. Searson and coworkers have constructed
high charge density conducting polypyrrole/graphite fiber com-
posite electrodes for battery applications [27].
More recently, Svec’s group have synthesized microporous
polypyrroles by using N-alkylation with iodo compounds to
hypercrosslink the nonporous precursor [30]. To our knowledge
there are no literature reports on the synthesis of microporous
* Corresponding author. Tel.: þ86 431 85262118; fax: þ86 431 85262117.
E-mail address: sbzhang@ciac.jl.cn (S. Zhang).
0032-3861/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymer.2013.04.038

Y. Yang et al. / Polymer 54 (2013) 3254e3260
3255
polypyrrole networks directly from pyrrole-containing monomers
using an oxidative polymerization process. Herein, we describe the
synthesis of pyrrole-containing polymers by oxidative polymeri-
zation of two novel monomers, namely Tetrakis(4-(N-(tert-butox-
ycarbonyl)-pyrrole)phenyl)methane (TNPM) and 1,3,5-tri(4-(N-
(tert-butoxycarbonyl)-pyrrole)phenyl)benzene (TNPP).
8 H), 7.26 (d, J ¼ 8.0 Hz, 8 H), 6.27 (s, 8 H), 1.29 (s, 36 H). 13C NMR
(600 MHz, CDCl3, d): 149.92, 145.93, 134.96, 132.37, 130.58, 128.67,
123.22, 115.03, 110.98, 84.10, 64.85, 28.05.
2.2.2. Synthesis of 1,3,5-tri(4-(N-(tert-butoxycarbonyl)-pyrrole)
phenyl)benzene (TNPP)
TNPP was synthesized by the reaction of 1,3,5-tri(4-bromophenyl)
benzene and N-(tert-butoxycarbonyl)-pyrrol-2-ylboronic acid ac-
2. Experimental
cording to the same method. 1H NMR (400 MHz, DMSO-d6,
d
): 7.90
(s,3H), 7.75(d, J¼ 8.0Hz,6H),7.53(d,J¼ 8.0Hz,6H),7.44(s, 3H), 6.32
(s, 6 H), 1.47 (s, 18 H). 13C NMR (600 MHz, CDCl3,
): 149.79, 142.52,
2.1. Materials
d
140.26, 135.31, 134.09, 126.92, 125.44, 123.19, 115.08, 111.10, 110.39,
84.14, 28.10.
Tetrakis(4-bromophenyl)methane (TPM) and 1,3,5-tri(4-bromo-
phenyl)benzene were prepared according to reported methods
[11,31]. N-(tert-butoxycarbonyl)-pyrrol-2-ylboronic acid and
Pd(PPh3)4 were purchased from Sigma Aldrich and used as
received. CH2Cl2 (DCM) was dried over CaH2 prior to use. Anhy-
drous potassium carbonate was finely powdered prior to use. Other
chemicals were used as received.
2.3. Synthesis of microporous polypyrroles
Microporous polypyrroles were synthesized by oxidative
coupling polymerization of the tert-butoxycarbonyl-protected
monomers promoted by anhydrous FeCl3. The polymers prepared
from TNPM and TNPP are denoted as PTNPM and PTNPP, respec-
tively. Polymeric films prepared from TNPM and TNPP are named as
PTNPM-F and PTNPP-F, respectively. The representative prepara-
tions for PTNPM and PTNPM-F are given in detail as follows.
2.2. Synthesis of monomers
2.2.1. Synthesis of tetrakis(4-(N-(tert-butoxycarbonyl)-pyrrole)
phenyl)methane (TPNM)
To a solution of tetrakis(4-bromophenyl)methane (0.6360 g,
1
mmol) and N-(tert-butoxycarbonyl)-pyrrol-2-ylboronic acid
2.3.1. The preparation of PTNPM
(1.0128 g, 4.8 mmol) in 30 mL of THF was added 10 mL of a satu-
rated aqueous solution of potassium carbonate, and then degassed
by bubbling nitrogen gas for 15 min. After adding Pd(PPh3)4 (57 mg,
0.05 mmol) under a nitrogen atmosphere, the reaction mixture was
stirred at 80 ꢁC for 12 h, and then cooled to room temperature. The
resulting mixture was extracted with ethyl acetate three times. The
combined organic layer was washed with deionized water and
dried over sodium sulfate. After concentration under reduced
pressure, the residual oil was purified by column chromatography
using n-hexane: ethyl acetate (30: 1) as the eluent to give the
desired product as a light yellow solid in 81% yield. 1H NMR
PTNPM was prepared by following an analogous procedure for
the synthesis of CPOP-1 [23]. To the solution of TNPM (0.196 g,
0.2 mmol) in 20 mL of anhydrous CH2Cl2 was added anhydrous
FeCl3 (156 mg, 0.96 mmol) under a nitrogen atmosphere. The so-
lution mixture was stirred at room temperature for 48 h. Then
100 mL of methanol was added to the reaction mixture and the
resulting mixture was stirred for 1 h. The brown precipitate ob-
tained was filtered and successively washed with water, methanol,
and CH2Cl2. After extraction in a Soxhlet extractor with methanol
for 24 h, and then with THF for another 24 h, the desired polymer
was collected and dried in a vacuum oven at 120 ꢁC for 24 h and
190 ꢁC for 1 h (83% yield).
(400 MHz, DMSO-d6,
d
): 7.35 (t, J ¼ 2.0 Hz, 4 H), 7.30 (d, J ¼ 8.0 Hz,
Scheme 1. Synthesis of monomers and polymeric networks.

3256
Y. Yang et al. / Polymer 54 (2013) 3254e3260
2.3.2. The preparation of PTNPM-F
Japan) at an accelerating voltage of 6.0 kV and equipped with a
Horiba energy dispersive X-ray spectrometer. Volumetric gas
adsorption was performed on an Autosorb-1 instrument (Quan-
tachrome). Nitrogen adsorption isotherms at 77 K were measured
in liquid-nitrogen baths. P and P0 are the vapor pressure of the
adsorbate in adsorption measurements and the saturated vapor
pressure of the adsorbate, respectively, and P/P0 denotes the rela-
tive pressure of the adsorbate.
5 mL of CF3COOH was added dropwise to the solution of TNPM
(0.196 g, 0.2 mmol) in 5 mL of anhydrous CH2Cl2 at 0 ꢁC under ni-
trogen in about 2 min. The solution mixture was stirred for 1 h and
then transferred to a preheated glass dish where the polymeriza-
tion occurred, followed by solvent evaporation yielding a black, thin
film. The film was dipped in 0.5 M NaOH solution for 24 h to remove
the excess CF3COOH. After the film was washed with water and
methanol several times, it was dried in a vacuum oven at 120 ꢁC for
24 h (93% yield).
3. Results and discussion
2.4. Characterization
3.1. Synthesis and characterization
Solution-state 1H NMR and 13C NMR spectra were recorded on a
Bruker Avance 400 MHz and 600 MHz spectrometer, respectively.
Chemical shifts are reported in ppm downfield from SiMe4. Solid-
state NMR spectra were obtained on a Chemagnetics CMS-400
spectrometer. Powder X-ray diffraction data were collected using
The monomers were synthesized from the Suzuki reaction of
the corresponding poly bromo aryl hydrocarbons and N-(tert-
butoxycarbonyl)-pyrrol-2-ylboronic acid, as shown in Scheme 1.
The yield of the reaction was about 80%, and the proposed
structure was confirmed from 1H NMR, 13C NMR and FT-IR spectra
(Fig. 1). The FT-IR spectra showed a disappearance of the CeBr
vibration of tetrakis(4-bromophenyl)methane at 511 cmꢀ1 and the
appearance of the characteristic absorption bands of pyrrole in the
700e1600 cmꢀ1 range (i.e., 1500, 1370, 1250 and 875 cmꢀ1 were
a Bruker D8-ADVANCE qe2q diffractometer. The FT-IR spectra were
obtained using a Bruker Vertex 70 spectrometer at a nominal res-
olution of 2 cmꢀ1. TGA wasꢀp1erformed on a PU 4K (Rigaku) at a
heating rate of 10 ꢁC min
with N2 as carrier gas. Size and
morphology of the samples were observed under a field-emission
scanning electron microscope (HitachiS-4800). SEM observations
were carried out using a Hitachi S-4800 microscope (Hitachi Ltd.,
Fig. 1. FT-IR spectra of TPM, TNPM and PTNPM (top) and TNPP, PTNPP and PTNPP-F
(bottom).
Fig. 2. Solid-state 13C NMR spectrum for PTNPM (top) and PTNPP (bottom).

Y. Yang et al. / Polymer 54 (2013) 3254e3260
3257
considered to be the result of pyrrole ring stretching vibration,
CeN stretching vibration and ]CeH in-plane deformation vibra-
tion, respectively) [32]. In addition, the appearance of a typical
absorption bands of pyrrole in the 700e1600 cmꢀ1 range were
found, which meant the pyrrole ring remained unaffected during the
polymerization. The almost disappearance of the absorption band
for e(C]O)e absorption at 1750 cmꢀ1 and appearance of the broad
peak for NeH absorptions at 3400 cmꢀ1 indicated the deprotection
of the pyrrole moieties in the polymer. The structure of the networks
has been characterized at the molecular level by 13C solid-state NMR
and the signal assignments for the spectra are displayed in Fig. 2. The
13C solid-state NMR confirmed the presence of sp2 carbons from the
pyrrole and benzene as well as sp3 carbon from methyl in tetrakis-
phenylmethane containing network. The scanning electron micro-
graph showed that the polymeric networks consisted of fused
spheres with diameters of 100 nm for PTNPM (Fig. 3a) and 50 nm for
PTNPP (Fig. 3b).
Thermo gravimetric analysis (TGA) indicated that the polymer
networks remained stable upto 300 ꢁC (Fig. 4). The polymers were
also stable towards water, base and acid. For instance, there was
negligible change in the FT-IR spectra of PTNPM after dipping in
1 M HCl for 2 days or 1 M NaOH for 30 days at room temperature
(Fig. S2).
absorption band for e(C]O)e absorption at around 1750 cmꢀ1
,
indicated the successful cross-linking of the two reagents. The
molecular weight measured by MS matched with the proposed
structure, which also confirmed the successful synthesis of the
monomers.
The microporous polymeric networks were synthesized by
oxidative coupling polymerization promoted by anhydrous FeCl3.
This reaction produced brown powdery compounds, which had a
low density and were not soluble in any of the common organic
solvents. For purification, the samples were successively washed
with water, methanol, and CH2Cl2 to remove solvent residues and
starting materials, and were finally heated at 120 ꢁC for 24 h under
vacuum to remove volatile entities. PTNPM and PTNPP were also
heated at 190 ꢁC for 1 h to thermally deprotect the pyrrole units [33].
The polymers were amorphous as evidenced by powder X-ray
diffraction analysis (Supporting Information, Fig. S1). They were also
characterized from their FT-IR spectra (Fig. 1). The characteristic
Fig. 3. SEM image showing fused spheres in the PTNPM (a) and PTNPP (b); (c) Photograph of PTNPM-F; (d) SEM image showing the smooth surface of PTNPM-F; (e and f) Cross-
sectional morphologies of PTNPM-F.

3258
Y. Yang et al. / Polymer 54 (2013) 3254e3260
isotherms according to the IUPAC classification [34]. The high up-
take at very low pressures indicated high microporosity. With the
increase of pressure, the nitrogen uptake increased, which indi-
cated a high external surface area due to the presence of very small
particles [35]. Listed in Table 1 are the key structural properties
derived from the sorption isotherm data, such as BET and Langmuir
specific surface area, micropore specific area, total volume, and
micropore volume. The BET surface area of PTNPM (1408 m2 gꢀ1
)
was higher than that of PTNPP (828 m2 gꢀ1). This can be attributed
to the default diamondoid framework topology imposed by the
tetrahedral monomer, which provides wide openings and inter-
connected pores to efficiently eliminate “dead space” [36,37]. The
pore size calculated from nonlinear density functional theory
(NLDFT) gave a value of about 1.7 nm for PTNPM and 1.4 nm for
PTNPP (Fig. 5).
The high surface area and the microporous nature of the poly-
mers prompted us to study their CO2 sorption properties. Fig. 6
shows the CO2 isotherms of the networks measured at 273 K. The
CO2 sorption was completely reversible and no significant hysteresis
was observed. At 1 bar, the CO2 uptake of PTNPM and PTNPP reached
values of 2.69 and 1.96 mmol gꢀ1, respectively. As a comparison of
the adsorption efficiency, BPL carbon (SBET ¼ 1150 m2 gꢀ1; a common
reference material for CO2 uptake) exhibited an uptake of
1.9 mmol gꢀ1 at 1 bar and 273 K [38,39]. The covalent organic
Fig. 4. TGA curves of microporous polymer networks.
3.2. Gas adsorption studies
The pore structures of the networks were evaluated by nitrogen
sorption isotherms (Fig. 5) measured at 77 K, and the two networks
exhibited a combination of type I and II reversible sorption
framework, COF-102 (SBET ¼ 3620 m2
g
ꢀ1) showed a CO2 uptake of
1.56 mmol gꢀ1 at 1 bar and 273 K [40]. As an additional reference,
PAF-1 (SBET ¼ 4077 m2 gꢀ1) adsorbed 2.65 mmol gꢀ1 under the same
conditions. The correlation between CO2 uptake capacities and the
surface areas is not proportional, and chemical functionality also
plays a significant role [17,41]. For our system, the high density of
pyrrole functionalities makes the polymers electron-rich, which
enhances the interaction between CO2 and the polymers [23],
resulting in their relatively high CO2 uptake capacities.
3.3. Preparation and properties of microporous films
The crucial factor that determines the performance of photo-
electric devices is the quality of thin films. However, most of the
microporous polymeric networks synthesized till date are intrac-
table solids and processability of the networks into thin films is
difficult [42]. In this context, the production of microporous
network membranes using traditional methods which requires the
formation of a polymer solution and subsequent solvent evapora-
tion is limited [43,44]. Microporous network films can be synthe-
sized by applying techniques similar to solegel processes that
entail a polymerization and a concurrent solvent evaporation pro-
cess [43]. Recently, Dai and coworkers have developed a facile
synthesis of triazine-framework-based porous membranes (TFMs)
for CO2 separation through superacid-catalyzed cross-linking re-
actions [43]. However till date, no electroactive microporous
polymer prepared by this method has been reported. As 1H-pyrrole
can self-polymerize in the presence of acid, we have prepared the
microporous network films (PTNPM-F and PTNPP-F) through an
acid catalyzed solegel process. Scheme 2 shows the synthetic
protocol for the formation of PTNPM-F film. Trifluoroacetic acid
(CF3COOH) was added to the solution of TNPM in DCM under a
nitrogen atmosphere. After stirring at 0 ꢁC for 1 h, the transparent
solution became viscous and was transferred to the glass dish
which had been preheated to 40 ꢁC. At this stage, self-
polymerization of the deprotected TNPM had started. The wet
film on the glass dish was heated at 80 ꢁC for 40 min for further
polymerization and a concurrent solvent evaporation process,
yielding the film PTNPM-F. The film could automatically peel off
from the glass dish, to become a free-standing film as shown in
Fig. 3c for PTNPM-F.
Fig. 5. Nitrogen adsorptionedesorption isotherms of microporous polymeric networks
measured at 77 K (top); Pore size distribution of microporous polymeric networks
(bottom). (The adsorption and desorption branches are labeled with filled and open
symbols, respectively.)

Y. Yang et al. / Polymer 54 (2013) 3254e3260
3259
Table 1
Porosity properties of microporous polymers.
Network
SBETa(m2 gꢀ1
)
SLanga(m2 gꢀ1
)
Smicroa(m2 gꢀ1
)
Vporea(cm3 gꢀ1
)
SBETb(m2 gꢀ1
)
SLangb(m2 gꢀ1
)
Vporeb(cm3 gꢀ1
)
CO2 uptakeb(mmol gꢀ1
)
PTNPM
PTNPP
PTNPM-F
PTNPP-F
1408
828
29
2109
1248
65
807
542
0
1.58
0.63
0.058
0.013
678
474
570
593
765
538
679
770
0.081
0.054
0.051
0.050
2.69
1.96
1.60
1.17
4
9
0
a
Data calculated from N2 sorption isotherms at 77 K.
Data calculated from CO2 sorption isotherms at 273 K.
b
As shown in Fig. 1, PTNPP and PTNPP-F possess similar FT-IR
spectra, which indicate that they have almost identical chemical
structures even though they were synthesized by different meth-
odologies. However, the films contained a small residue of tri-
fluoroacetate anions in their networks even though they were
dipped in 0.5 M NaOH for 24 h and washed thoroughly with water
and methanol (Fig. S3). The surface scanning electron micrographs
showed that the films had smooth and uniform surfaces (Fig. 3d). In
order to further investigate the morphology of the films, cross-
sectional SEM images of PTNPM-F was taken, as shown in Fig. 2e
and f. PTNPM-F, with a thickness of 16 mm, consists of compact
nano-size granules without any obvious inter-particulate porosity.
Unfortunately, the films were effectively nonporous to nitrogen at
77 K (with the BET surface areas of 29 m2 gꢀ1 for PTNPM-F and
4 m2 gꢀ1 for PTNPP-F), suggesting limited N2 uptake at that tem-
perature. This can be attributed either to the absence of inter-
particle porosity used to transport N2 molecules into the films
[45] or the restricted access of N2 molecules within the narrow
microporosity (<0.7 nm) [46]. In contrast, the adsorption of CO2 at
273 K offers a valuable complementary technique to analyze the
microporosity, in particular the narrow microporosity [47,48].
Therefore, the permanent porosity of the films was measured by
CO2 sorption at 273 K (Fig. 6). As summarized in Table 1, the BET
surface areas calculated from CO2 sorption isotherms were
570 m2 gꢀ1 for PTNPM-F and 593 m2
g
ꢀ1 for PTNPP-F, which were
ꢀ1),
similar to that of PTNPM (678 m2 ꢀ1) and PTNPP (474 m2
g
g
even though the latter pair had much higher BET surface areas
calculated from N2 sorption isotherms. In addition, the CO2 sorption
isotherms of the films had obvious hysteresis, while their “pow-
dery” counterparts had reversible sorption isotherms. All these
results could be explained by the narrower microporosity in the
films. The CO2 uptake capacities of films (1.60 mmol gꢀ1 for PTNPM-
F and 1.17 mmol gꢀ1 for PTNPP-F) were lower than that of their
“powdery” counterparts (2.69 mmol gꢀ1 for PTNPM and
1.96 mmol gꢀ1 for PTNPP). This can be attributed to the presence of
residual trifluoroacetate anions in the films, which in a way, led
to the decrease of free NeH’s in the structure and the crowding of
the pores.
Fig. 6. CO2 adsorption (closed)/desorption (open) isotherms of powders (top) and
films (bottom) at 273 K.
Scheme 2. Schematic diagram for the synthesis of PTNPM-F by the solegel process.

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Y. Yang et al. / Polymer 54 (2013) 3254e3260
[14] Kuhn P, Kruger K, Thomas A, Antonietti M. Chem Commun 2008;44:5815.
4. Conclusion
[15] Kaur P, Hupp JT, Nguyen ST. ACS Catal 2011;1:819.
[16] Xie Z, Wang C, deKrafft KE, Lin W. J Am Chem Soc 2011;133:2056.
[17] Dawson R, Stöckel E, Holst JR, Adams DJ, Cooper AI. Energy Environ Sci
2011;4:4239.
[18] Farha OK, Spokoyny AM, Hauser BG, Bae YS, Brown SE, Snurr RQ, et al. Chem
Mater 2009;21:3033.
Two types of microporous polymeric networks have been pre-
pared from pyrrole-containing monomers by FeCl3-mediated
oxidative coupling polymerization. The polymeric networks
remained stable up to 300 ꢁC and were also stable towards water,
base and acid. PTNPM and PTNPP exhibited BET surface areas of 828
[19] (a) Uribe-Romo
J Fernando, Hunt JR, Furukawa H, Klock C, O’Keeffe M,
Yaghi OM. J Am Chem Soc 2009;131:4570;
and 1408 m2 gꢀ1
, with CO2 uptake capacities of 1.96 and
(b) Wu D, Xu F, Sun B, Fu R, He H, Matyjaszewski K. Chem Rev 2012;112:3959.
[20] Kim M, Byeon M, Bae JS, Moon SY, Yu G, Shin K, et al. Macromolecules
2011;44:7092.
[21] Pandey P, Farha OK, Spokoyny AM, Mirkin CA, Kanatzidis MG, Hupp JT, et al.
J Mater Chem 2011;21:1700.
[22] (a) Schmidt J, Weber J, Epping JD, Antonietti M, Thomas A. Adv Mater
2009;21:702;
(b) Chen Q, Wang JeX, Yang F, Zhou D, Bian N, Zhang XeJ, et al. J Mater Chem
2011;21:13554.
[23] Chen Q, Luo M, Hammershj P, Zhou D, Han Y, Laursen BW, et al. J Am Chem
Soc 2012;134:6084.
2.69 mmol gꢀ1 at 273 K and 1 bar, respectively. Microporous
polymeric films, with BET surface areas of 570 and 593 m2 gꢀ1, were
constructed through in situ deprotection and polymerization of
monomers using a solegel process on a flat glass dish catalyzed by
trifluoroacetic acid. Further applications in the area of energy
storage and CO2 separation for the microporous films are currently
being explored in our lab.
[24] Omastova M, Trchova M, Kovarova J, Stejskal J. Synth Met 2003;138:447.
[25] Armes SP. Synth Met 1987;15:61.
[26] Qi GJ, Huang LY, Wang HL. Chem Commun 2012;48:8246.
Acknowledgments
[27] Coffey B, Madsen PV, Poehler TO, Searson PC.
142:321.
[28] Hughes M, Shaffer MSP, Renouf AC, Singh C, Chen GZ, Fray DJ, et al. Adv Mater
2002;14:382.
[29] Hughes M, Chen GZ, Shaffer MSP, Fray DJ, Windle AH. Chem Mater 2002;14:1610.
[30] Germain J, Frechet JMJ, Svec F. Chem Commun 2009;12:1526.
[31] Zhao Y, Li J, Li C, Yin K, Ye D, Jia X. Green Chem 2010;12:1370.
[32] Jang J, Yoon H. Chem Commun 2003;6:720.
J Electrochem Soc 1995;
This research was financially supported by the National Basic
Research Program of China (No. 2012CB932802), the National Sci-
ence Foundation of China (No. 51133008, 51021003), and the Na-
tional high Technology Research and Development Program of
China (No. 2012AA03A601).
[33] Van Haare JAEH, Groenendaal L, Peerlings HWI, Havinga EE, Vekemans JAJM,
Janssen RAJ, et al. Chem Mater 1995;7:1984.
[34] Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquérol J, et al.
Pure Appl Chem 1985;57:603.
[35] Rose M, Bohlmann W, Sabo M, Kaskel S. Chem Commun 2008;44:2462.
[36] Lu WG, Yuan DQ, Zhao D, Schilling CI, Plietzsch O, Muller T, et al. Chem Mater
2010;22:5964.
Appendix A. Supplementary data
Supplementary data related to this article can be found online at
http://dx.doi.org/10.1016/j.polymer.2013.04.038.
[37] Trewin A, Cooper AI. Angew Chem Int Ed 2010;49:1533.
[38] Phan A, Doonan CJ, Uribe-Romo FJ, Knobler CB, Keeffe MO’, Yaghi OM. Acc
Chem Res 2010;43:58.
References
[39] Banerjee R, Furukawa H, Britt D, Knobler C, O’ Keeff M, Yaghi OM. J Am Chem
Soc 2009;131:3875.
[1] El-Kaderi HM, Hunt JR, Mendoza-Cortes JL, Cote AP, Taylor RE, O’Keeffe M,
et al. Science 2007;316:268.
[40] Furukawa H, Yaghi OM. J Am Chem Soc 2009;131:8875.
[41] (a) Torrisi A, Mellot-Draznieks C, Bell RG. J Chem Phys 2010;132:044705;
(b) Lim H, Cha MC, Chang JY. Polym Chem 2012;3:868.
[42] (a) Patra A, Koenen JM, Scherf U. Chem Commun 2011;47:9612;
(b) Preis E, Widling C, Scherf U, Patil S, Brunklaus G, Schmidt J, et al. Polym
Chem 2011;2:2186;
(c) Sprick RS, Thomas A, Scherf U. Polym Chem 2010;1:283.
[43] Zhu X, Tian C, Mahurin SM, Chai SeH, Wang C, Brown S, et al. J Am Chem Soc
2012;134:10478.
[2] Spitler EL, Dichtel WR. Nat Chem 2010;2:672.
[3] Colson JW, Woll AR, Mukherjee A, Levendorf MP, Spitler EL, Shields VB, et al.
Science 2011;332:228.
[4] Tsyurupa MP, Davankov VA. React Funct Polym 2006;66:768.
[5] Germain J, Hradil J, Frechet JMJ, Svec F. Chem Mater 2006;18:4430.
[6] Budd PM, Ghanem BS, Makhseed S, McKeown NB, Msayib KJ, Tattershall CE.
Chem Commun 2004;2:230.
[7] Du N, Park HB, Robertson GP, Dal-Cin MM, Visser T, Scoles L, et al. Nat Mater
2011;10:372.
[44] McKeown NB, Budd PM, Msayib KJ, Ghanem BS, Kingston HJ, Tattershall CE,
et al. Chem-Eur J 2005;11:2610.
[45] Mohanty P, Kull LD, Landskron K. Nat Commun 2011;2:401.
[46] Weber J, Antonietti M, Thomas A. Macromol Rapid Commun 2007;28:
1871.
[47] Weber J, Schmidt J, Thomas A, Bohlmann W. Langmuir 2010;26:15640.
[48] Zhu Y, Murali S, Stoller MD, Ganesh KJ, Cai W, Ferreira PJ, et al. Science
2011;332:1537.
[8] Weber J, Du N, Guiver MD. Macromolecules 2011;44:1763.
[9] Jiang JX, Su F, Trewin A, Wood CD, Niu H, Jones JTA, et al. J Am Chem Soc
2008;130:7710.
[10] Dawson R, Adams DJ, Cooper AI. Chem Sci 2011;2:1173.
[11] Ben T, Ren H, Ma SQ, Cao DP, Lan JH, Jing XF, et al. Angew Chem Int Ed
2009;48:9457.
[12] Ren H, Ben T, Wang ES, Jing XF, Xue M, Liu BB, et al. Chem Commun 2010;46:291.
[13] McKeown NB, Budd PM. Chem Soc Rev 2006;35:675.