Porphyrin-based porous polyimides: Synthesis, porous structure, carbon dioxide adsorption

Article abstract of DOI:10.1016/j.polymer.2019.02.062

A novel dianhydride 3,3^’-bis(3,4-dicarboxyphenoxy)-4,4^’-diphenylethynyl biphenyl dianhydride (BPEBPDA) and a new tetramine monomer 5,10,15,20- tetra[4-[(3-aminophenyl)ethynyl]phenyl]porphyrin (TAPEPP) were successfully synthesized. Porphyrin-based polyimides (PPBPIs) were synthesized from BPEBPDA and porphyrin-based building blocks (TAPP and TAPEPP) via polymerization reactions. The porphyrin-based porous polyimide networks (PPBPI-CRs) were obtained from PPBPIs through thermal crosslinking reactions. The PPBPI-CRs exhibited BET surface areas (682 m² g^?1 and 693 m² g^?1) and CO₂ uptakes (2.0 mmol g^?1 and 1.67 mmol g^?1 at 273 K and 1 bar) as well as the separation factors of CO₂/N₂ (37.63, 28.97) and CO₂/CH₄ (7.51, 5.61). Meanwhile, PPBPI-CRs showed an enhanced CO₂ isosteric enthalpies of adsorption (25.1 kJ mol^?1 and 30.1 kJ mol^?1) than other porous polymers.

Full text of DOI:10.1016/j.polymer.2019.02.062

Accepted Manuscript
Porphyrin-based porous polyimides: Synthesis, porous structure, carbon dioxide
adsorption
Kaixiang Shi, Ningning Song, Yongcun Zou, Shiyang Zhu, Haiwei Tan, Ye Tian, Bo
Zhang, Hongyan Yao, Shaowei Guan
PII:
S0032-3861(19)30202-2
DOI:
https://doi.org/10.1016/j.polymer.2019.02.062
JPOL 21301
Reference:
To appear in: Polymer
Received Date: 17 October 2018
Revised Date: 23 February 2019
Accepted Date: 27 February 2019
Please cite this article as: Shi K, Song N, Zou Y, Zhu S, Tan H, Tian Y, Zhang B, Yao H, Guan S,
Porphyrin-based porous polyimides: Synthesis, porous structure, carbon dioxide adsorption, Polymer
(2019), doi: https://doi.org/10.1016/j.polymer.2019.02.062.
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ACCEPTED MANUSCRIPT
Graphical Abstract

ACCEPTED MANUSCRIPT
Porphyrin-based porous polyimides: Synthesis, porous structure,
carbon dioxide adsorption
Kaixiang Shi a, Ningning Song a, Yongcun Zou c, Shiyang Zhu a, Haiwei Tan a, Ye
Tian a, Bo Zhang a, Hongyan Yao b,** and Shaowei Guan a,*
Key Laboratory of High Performance Plastics (Jilin University), Ministry of
a
Education, National & Local Joint Engineering Laboratory for Synthesis Technology
of High Performance Polymer, Jilin University, Qianjin Street 2699, Changchun,
130012, People’s Republic of China.
b Department of Materials Science and Engineering, National University of Singapore,
Singapore 117574, Singapore.
c
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of
Chemistry, Jilin University, Changchun 130012, China.
* Corresponding author. ** Corresponding author. E-mail address:guansw@jlu.edu.cn,
mseyaoh@nus.edu.sg.
Abstract: A novel dianhydride 3,3’-bis(3,4-dicarboxyphenoxy)-4,4’-diphenylethynyl
biphenyl dianhydride (BPEBPDA) and a new tetramine monomer 5,10,15,20-
tetra[4-[(3-aminophenyl)ethynyl]phenyl]porphyrin (TAPEPP) were successfully
synthesized. Porphyrin-based polyimides (PPBPIs) were synthesized from BPEBPDA
and porphyrin-based building blocks (TAPP and TAPEPP) via polymerization
reactions. The porphyrin-based porous polyimide networks (PPBPI-CRs) were
obtained from PPBPIs through thermal crosslinking reactions. The PPBPI-CRs
exhibited BET surface areas (682 m2 g-1 and 693 m2 g-1) and CO2 uptakes (2.0 mmol
g-1 and 1.67 mmol g-1 at 273 K and 1 bar) as well as the separation factors of CO2/N2
(37.63, 28.97) and CO2/CH4 (7.51, 5.61). Meanwhile, PPBPI-CRs showed an
enhanced CO2 isosteric enthalpies of adsorption (25.1 kJ mol-1 and 30.1 kJ mol-1) than
other porous polymers.
Keywords
Porphyrin-based porous polyimides; Crosslinking reaction; Carbon dioxide adsorption
1. Introduction
Porous organic polymers (POPs) are a class family of functional polymers with large
surface areas, desirable pore sizes and outstanding properties. POPs have attracted a
lot of attentions due to their diverse potential applications in gas storage and
separation [1], heterogeneous catalysis [2,3], dye adsorption [4] and sensor [5], etc.
Over the past decades, various POPs including polymers of intrinsic microporosity
(PIMs) [6], covalent organic frameworks (COFs) [7,8], conjugated micro- and
mesoporous polymers (CMPs) [9], hyper crosslinked polymers (HCPs) [10] and
porous aromatic frameworks (PAFs) [11,12] have been developed.
Normally, POPs are constructed from rigid compounds via various reactions [13,14].

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Among the POPs, porous polyimides (PPIs) are a kind of high performance polymers
featuring with large specific surface areas, high small gas molecules adsorption
capacities, excellently thermal and chemical stabilities [15,16]. Porphyrin and its
derivatives with two-dimensional (2D) and large π systems offer well-defined planar
and rigid building blocks. Rigid porphyrin-based building blocks are a kind of ideal
candidates for constructing porous organic frameworks. Porphyrin-based porous
polymers can exhibit large BET surface areas, high CO2 capture capacities and
excellent catalytic performances [15,17,18]. Taking advantage of the combination of
imide linkages and porphyrin-based groups can endow aromatic polymers with porous
structures and introduce more nitrogen atoms which is beneficial to carbon dioxide
adsorption.
In general, PPIs including crystalline and amorphous porous polymers [19,20], are
constructed from rigid aromatic compounds via traditional polymerization reactions.
Unlike rigid and robust porous polyimides, most hyperbranched polyimides (HBPIs)
prepared via traditional polycondensation reactions have flexible skeletons, which
causes the dense stacking and collapsing of the pore structures, thus these HBPIs do
not have microporous structures. Crosslinked structures can be introduced to fix the
three-dimensional networks and induce the formation of pore structures in the
hyperbranched polyimides [21,22]. As reported, the crosslinking density in the
networks had a significant effect on the pore sizes and BET surface areas of resultant
polycyanurate networks [23]. It is a potential way to tune the porosity parameters of
crosslinked hyperbranched polyimides by adjusting the crosslinking densities of
alkynyl
groups.
For
the
purpose,
two
tetramine
monomers
(TAPP),
5,10,15,20-tetra(4-aminophenyl)porphyrin
5,10,15,20-tetra[4-[(3-aminophenyl)ethynyl]phenyl]porphyrin (TAPEPP) and a novel
dianhydride monomer 3,3’-bis(3,4-dicarboxyphenoxy)-4,4’-diphenylethynyl biphenyl
dianhydride (BPEBPDA) were designed and successfully synthesized. TAPEPP and
BPEBPDA contained crosslinkable alkynyl groups, but TAPP did not have C≡C. In
the present work, in order to study the effect of crosslinking density on the porosity
parameters of PPBPI-CRs, firstly, two porphyrin-based hyperbranched polyimides
with different crosslinkable alkynyl densities were synthesized using these monomers,
subsequently, the porphyrin-based crosslinked polyimides (PPBPI-CRs) were
prepared via crosslinking reactions. Their porosity parameters and carbon dioxide
uptakes as well as the separations of CO2/N2 and CO2/CH4 were fully investigated.
2. Result and discussion
2.1. Synthesis and characterization of polymers
A novel dianhydride (BPEBPDA) containing two crosslinkable pendant alkynyl
groups and a tetramine with alkynyl functional groups and porphyrin unit were
designed
3,3’-bis(3,4-dicarboxyphenoxy)-4,4’-diphenylethynyl
(BPEBPDA) was obtained via
and
synthesized.
As
illustrated
in
Scheme
1,
biphenyl
dianhydride
a
five-step chemical reaction. Firstly,

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3,3’-dihydroxy-4,4’-diaminobiphenyl was reacted with sodium nitrite in the presence
of hydrobromic acid via Sander Maier reaction to give 4,4’-dibromobiphenyl-3,3’-diol
(I). Subsequently, 3,3'-bis(3,4-dicyanophenoxy)-4,4’-dibromo biphenyl (II) was
obtained from I and 4-nitrophthalonitrile via nucleophilic substitution reaction.
3,3'-Bis(3,4-dicyanophenoxy)-4,4’-diphenylethynyl biphenyl (III) was synthesized
from II and phenylacetylene via Sonogashira coupling reaction using PdCl2(PPh3)2
and CuI as catalysts. 3,3'-Bis(3,4-dicyanophenoxy)-4,4’-diphenylethynyl biphenyl was
hydrolyzed in the presence of potassium hydroxide solution to give the carboxylic
monomer
(IV).
The
final
target
product
3,3’-bis(3,4-dicarboxyphenoxy)-4,4’-diphenylethynyl biphenyl dianhydride (V) was
obtained from IV via dehydration reaction in a mixture solution of acetic acid and
acetic anhydride. 5,10,15,20-Tetra(4-aminophenyl) porphyrin (TAPP) was prepared
according
to
the
literature
(in
the
ESI*).
5,10,15,20-Tetra[4-[(3-aminophenyl)ethynyl]phenyl]porphyrin (TAPEPP) was a novel
polyamine containing porphyrin building block and crosslinkable alkynyl groups.
TAPEPP (Scheme 2) was
synthesized via
a
two-step
reaction.
5,10,15,20-Tetra(4-bromophenyl) porphyrin (H2TPPBr4) was produced by
Alder-Longo reaction, and the final product was collected via Sonogashira Hagiwara
coupling reaction. The resultant dianhydride and porphyrin-based monomers were
characterized by FTIR, 1H NMR, 13C NMR (Fig. S1, S2, S4, S5, S6, S7 in the ESI*).
Scheme 1 Synthesis route to BPEBPDA.

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Scheme 2 Synthesis route to TAPEPP.
Scheme 3 Synthesis routes to the porphyrin-based porous polyimide networks.
A series of porphyrin-based hyperbranched polyimides (PPBPI-1 and PPBPI-2)
were prepared from BPEBPDA and two types of tetramine monomers (TAPP and

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TAPEPP) via polymerization reactions (Scheme 3). Subsequently, the crosslinked
hyperbranched polyimides (PPBPI-1-CR and PPBPI-2-CR) were obtained from
crosslinking reactions.
For PPBPIs, the significant stretching bands in the FT-IR spectra (Fig. S3 in the
ESI*) at 3310 cm-1 were attributed to the porphyrin rings, demonstrating the
successful incorporation of porphyrin units within polymer skeletons. The strong
absorption bands at 1776 cm-1 and 1722 cm-1 were assigned to the carbonyl
asymmetrical and symmetrical stretching, indicative of the formation of
polyimides and the consumption of tetramines and dianhydride. The characteristic
absorption bands existed in the FT-IR spectra at 2212 cm-1 were on account of the
presence of alkynyl groups. Meanwhile, compared with PPBPI-1, there was a
more intense band around 2212 cm-1 in the spectrum of PPBPI-2, it was ascribed
to more alkynyl groups existing in both dianhydride and TAPEPP monomers. For
PPBPI-CRs, the characteristic bands at 2212 cm-1 disappeared, indicating that
PPBPI-CRs had undergone crosslinking reactions. The disappearance of
absorption bands at 3310 cm-1 could be due to the fracture of N-H bonds of
porphyrin structures accompanying with the crosslinking reactions.
Fig. 1 13C CP/MAS NMR spectra of samples.
Fig. 2 FE-SEM images of PPBPI-1 (2a), PPBPI-2 (2b), PPBPI-1-CR (2c),

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PPBPI-2-CR (2d). Scale bar: 500 nm.
The 13C CP-MAS NMR spectra of PPBPIs and PPBPI-CRs were illustrated in Fig. 1.
The resonance bands at 164 ppm were assigned to the carbonyl carbons, the aromatic
carbons and the carbons of porphyrin rings located at the overlapping resonance bands
from 110 to 155 ppm. The signal bands at 96, 90 and 84 ppm were attributed to the
carbons of alkynyl groups for PPBPIs [24,25]. The absence of resonance bands of
alkynyl carbons in PPBPI-CRs suggested that PPBPI-CRs had undergone crosslinking
reactions. As shown in Table S1, the elemental analysis data was in accordance with
the theoretical values.
DSC analysis was used to study the crosslinking behaviors of the alkynyl groups in
the PPBPIs (Fig. S8 in the ESI*). The disappearance of exothermic peaks which were
attributed to the alkynyl groups indicated that the crosslinking reactions of
PPBPI-CRs were complete.
The PPBPI-CRs had outstanding chemical and thermal stabilities. They were not
dissolved in common organic solvents such as N,N-dimethyl formamide,
1-methyl-2-pyrrolidinone, acetone, tetrahydrofuran and chloroform due to the
crosslinked structures [26]. Besides, PPBPI-CRs were also stable in acidic and
alkaline solutions. TGA analysis (Fig. S9 in the ESI*) was conducted under a
nitrogen atmosphere to evaluate the thermal stabilities of all the polymers. As
illustrated in the TGA analyses curves, PPBPI-CRs had high 5% thermal
decomposition temperatures above 500 oC and high residues of more than 60% at
o
800 C. The slight loss at around 200 oC might be originated from the gas or
solvents absorbed in the PPBPI-CRs skeletons [27].
Powder X-ray diffraction of PPBPIs and PPBPI-CRs (Fig. S10 in the ESI*) were
studied and exhibited amorphous nature characteristic of polymers [28,29]. The
surface morphologies of PPBPIs and PPBPI-CRs were measured by
field-emission scanning electron microscopy (Fig. 2, and Fig. S13 in the ESI*).
As shown in Fig. 2, the samples showed rough surfaces and irregular
morphologies, which were consisted of tight agglomerates of tiny nanoparticles.
Meanwhile, transmittance electron microscopy (in Fig. S11, S12, in the ESI*) was
studied to confirm the porous structures of PPBPI-CRs. The images revealed that
the micropore channels existed within the PPBPI-CRs networks [30].
2.2. The BET surface areas and pore size distribution of PPBPI-CRs
Brunauer-Emmett-Teller (BET) surface areas of PPBPI-CRs were investigated by
physical sorption of nitrogen in the liquid nitrogen irrigation at 77 K. The sorption
isotherms revealed porosity parameters of crosslinked polymer networks and
elucidated the characteristic of permanent micropores. As illustrated in Fig. 3, the
sorption isotherms belonged to the characteristic type I sorption curves according to
IUPAC classifications. The isotherms displayed a steep rise at a very low relative
pressure (P/P0 < 0.01), indicating that abundance of micropores existed in the
PPBPI-CRs skeletons [31]. And the distinct capillary hysteresis loops of sorption
isotherms exhibited the presence of mesopores in the pore channels and the

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swelling effect between PPBPI-CRs skeletons and nitrogen [32].
The BET surface areas of PPBPI-1-CR and PPBPI-2-CR were calculated to be 682 m2
g-1 and 693 m2 g-1, respectively. Simultaneously, the total pore volumes of PPBPI-CRs
revealed 0.429 cm3 g-1 and 0.457 cm3 g-1, respectively. It was reported that porous
structures of HBPI-CRs was mainly influenced by the crosslinked structures rather
than by the topological structures of polyamines [21]. TAPP and TAPEPP were both
porphyrin-based tetramine monomers offering rigid building blocks, but the numbers
of their alkynyl functional groups were different. In contrast to TAPP, TAPEPP had
four crosslinkable alkynyl groups linked with extended benzene rings through the
C≡C triple bonds. Therefore, PPBPI-2 had a higher crosslinking density of alkynyl
group than that of PPBPI-1, but the BET surface areas and the total pore volumes of
PPBPI-1-CR and PPBPI-2-CR were close to each other, which perhaps because steric
hindrance restricted the chain segment movement of crosslinkable alkynyl groups
within polymer skeletons [13]. Meanwhile, in Fig. 3, this clearly showed that
PPBPI-2-CR had more mesopores, which could account for the higher total pore
volume of PPBPI-2-CR than that of PPBPI-1-CR. However, PPBPI-1-CR possessed
more micropores, thus it had larger micropore surface area and higher micropore
volume than PPBPI-2-CR.
Fig. 3 (a) Adsorption (filled) and desorption (empty) isotherms of N2 at 77 K for

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PPBPI-CRs, (b) pore size distribution by DFT method.
Pore size distribution (PSD) was collected from nitrogen sorption isotherms at 77 K
by original Density Functional theory (DFT). The pore size distribution of
PPBPI-1-CR and PPBPI-2-CR were shown in Fig. 3, they had similar pore size
distribution including mesopores and ultramicropores. The pore diameters of
PPBPI-CRs (in Table 1) were around at 0.6 nm and 1.2 nm. The pores with bigger
sizes might come from the possible crosslinked structures formed during the
crosslinking reactions (Scheme. S1 in the ESI*) [33-36]. The pores with smaller sizes
could be derived from the hyperbranched polyimide skeletons [37]. The total pore
volumes of PPBPI-CRs were mainly ascribed to the micropores and mesopores
existing in the PPBPI-CRs networks, which was beneficial for carbon dioxide
adsorption.
Table 1 Specific surface area, pore volume, and pore size distribution in PPBPI-CRs
networks.
a
b
c
d
e
Samples
SBET
SLangmuir
m2 g-1
930
Smicro
Vtotal
Vmicro
PSDf
nm
m2 g-1
m2 g-1
cm3 g-1 cm3 g-1
PPBPI-1-CR
PPBPI-2-CR
682
332
0.429
0.457
0.155
0.147
0.59,1.27
693
1050
275
0.54,1.26
a,
b
The Brunauer-Emmett-Teller and Langmuir surface areas of samples were
calculated from the sorption isotherms of nitrogen.
c The micropore surface areas were collected basing on t-plot method.
d Total pore volume derived from N2 isotherms at P/P0 = 0.99.
e Micropore volume determined from t-plot method.
f Pore size distribution (PSD) was based on original density functional theory.
2.3. Carbon dioxide adsorption and selectivity of CO2/N2 and CO2/CH4 of
PPBPI-CRs
CO2 sorption isotherms (Fig. 4) were collected at 273 K and 295 K to calculate CO2
uptakes (in Table 2) and CO2 isosteric heats of adsorption (Qst). The CO2 uptakes of
PPBPI-1-CR and PPBPI-2-CR were 2.0 mmol g-1 and 1.67 mmol g-1 at 273K and 1
bar, respectively. The previous reports had revealed that N and O functionalities,
high micropore volumes and small micropore sizes facilitated the small gas
molecules adsorption capacities [23,38]. The CO2 uptakes of PPBPI-CRs could be
attributed to two reasons: first, there were N and O functionalities existing in the
crosslinked polymer skeletons; second, PPBPI-CRs had abundant micropores and
considerable micropore volumes. Compared with PPBPI-2-CR, the CO2 uptake of
PPBPI-1-CR was higher. The higher CO2 adsorption value of PPBPI-1-CR was
probably due to the larger micropore volume (0.155 cm-1 g-1) and the higher
micropore volume ratio (micropore volume/total pore volume = 0.361) than those of

ACCEPTED MANUSCRIPT
PPBPI-2-CR (0.147 cm-1 g-1, 0.322). Moreover, the CO2 uptake of PPBPI-1-CR was
comparable to or exceeded those of many other porous organic polymers with high
specific surface areas, such as PAF-1 (2.07 mmol g-1, 5640 m2 g-1) [39], COF-5 (1.34
mmol g-1, 1670 m2 g-1) [40], CMP-1 (2.05 mmol g-1, 837 m2 g-1) [41].
CO2 isosteric enthalpies of adsorption (Qst) (Fig. 5) were calculated at two different
temperatures by Clausius-Clapeyron equation to evaluate the interaction forces
between the crosslinked polymers and CO2 molecules. As illustrated in Table S2 (in
the ESI*), Q0, KH, and A0 were calculated by using LnP=Qst/RT+C and
d[LnKH]/dT=Q0/RT2, the KH and A0 values of PPBPI-1-CR exceeded those of
PPBPI-2-CR, respectively. Q0 is the enthalpy of adsorption and the indication of
binding affinity at zero coverage. The Qst isotherms revealed that PPBPI-2-CR had a
much higher Q0 (30.1 kJ mol-1) than those of PPBPI-1-CR (25.1 kJ mol-1) and other
porous organic polymers such as PAFs (15.6-27.8 kJ mol-1) [39], STPIs (28-36 kJ
mol-1) [42], and CMP-1 (26.8 kJ mol-1) [41]. PPBPI-2-CR had higher Q0 than
PPBBPI-1-CR, which meant PPBPI-2-CR had stronger binding affinity between
its crosslinked polymer skeleton and CO2. The higher Q0 of PPBPI-2-CR
compared to PPBPI-1-CR might be attributed to the porosities, network structures
and complexities of pore channels in the skeletons [43]. And the enhanced binding
affinity was probably attributed to the interaction of dipolar and quadrupolar between
CO2 guest molecules and porous networks [44]. Besides, the virial plots of CO2
adsorption for PPBPI-CRs at 273 and 295 K (Fig. 6) revealed good linear
relationships. The pore sizes calculated from CO2 sorption isotherms at 273 K were
centered at around 0.6 nm, indicative of the presence of ultramicropores within the
crosslinked polymer networks.
The sorption isotherms of N2 and CH4 at 273 K were measured and compared
with those of CO2 to calculate the separation properties of PPBPI-CRs (Fig. 7 and
Fig. S14). As reported, compared to N2 and CH4, CO2 had the stronger adsorption
ability with polymer skeletons, leading to the high separation factors of CO2/N2
and CO2/CH4 [37,43]. For PPBPI-1-CR, the separation factors of CO2/N2 and
CO2/CH4 from initial slopes of component sorption isotherms were 37.63 and
7.51, respectively, which were higher than those of PPBPI-2-CR (28.97 and 5.61).
The higher CO2/N2 and CO2/CH4 selectivities of PPBPI-1-CR compared to
PPBPI-2-CR were attributed to two reasons: first, PPBPI-1-CR possessed more
micropores and higher micropore volume, causing the higher CO2 uptake over N2 and
CH4 because of the molecular sieving effect; second, the content of nitrogen atoms in
PPBPI-1-CR was higher than that in PPBPI-2-CR, which was advantageous for the
affinity of PPBPI-1-CR skeleton toward CO2 [45].

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Fig. 4 (a) CO2 adsorption and desorption isotherms for PPBPI-CRs at 273 and
295 K, (b) pore size distribution for samples by density functional theory at 273
K.
Fig. 5 Variation of CO2 isosteric enthalpies of PPBPI-CRs with the adsorbed
amount.

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Fig. 6 Virial plots of CO2 adsorption from PPBPI-CRs at 273 and 295 K.
Fig. 7 Adsorption isotherms of CO2, N2 and CH4 gases at 273 K for PPBPI-CRs.
Table 2 CO2 uptakes and pore size distribution from CO2 sorption isotherms at 273 K,
gas selectivities from CO2, N2 and CH4 sorption isotherms at 273 K.
Samples
CO2 uptakea CO2 uptakeb
Pore sizec
nm
Gas selectivityd
CO2/N2 CO2/CH4
mmol g-1
2.0
mmol g-1
1.28
PPBPI-1-CR
PPBPI-2-CR
0.66
37.63
7.51
1.67
1.05
0.68
28.97
5.61
a CO2 uptakes derived from CO2 sorption isotherms at 1.0 bar and 273 K.
b CO2 uptakes determined at 1 bar and 295 K.
c Pore size distribution was collected from CO2 sorption isotherms at 273 K.
d The CO2/N2 and CO2/CH4 selectivities were calculated from initial slopes of
pure-component sorption isotherms.

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3. Conclusions
Two porphyrin-based porous hyperbranched polyimides (PPBPI-1-CR and
PPBPI-2-CR) were synthesized from a novel dianhydride (BPEBPDA) and two
porphyrin building blocks (TAPP and TAPEPP) via polymerization and subsequent
crosslinking reactions. PPBPI-CRs revealed specific surface areas (682 and 693 m2 g-1)
and pore sizes (0.6 and 1.2 nm). Although PPBPI-CRs had different crosslinking
densities of alkynyl groups, they exhibited similar BET surface areas due to steric
hindrance. The PPBPI-CRs exhibited CO2 uptakes (2.0 mmol g-1 and 1.67 mmol g-1)
and CO2 isosteric enthalpies (25.1 kJ mol-1 and 30.1 kJ mol-1) as well as the
separation factors of CO2/N2 (37.63, 28.97) and CO2/CH4 (7.51, 5.61).
Acknowledgements
We thank the National Nature Science Foundation of China (Grant no. 51573067) for
the financial support.
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ACCEPTED MANUSCRIPT
Highlights
•
Two porphyrin-based porous polyimides (PPBPI-1-CR and PPBPI-2-CR) were
synthesized via polymerization and post-crosslinking reactions.
•
PPBPI-CRs revealed specific surface areas (682 and 693 m2 g-1) and CO2 uptakes
(2.0 and 1.67 mmol g-1 at 273 K and 1 bar) as well as isosteric heats of adsorption
(25.1 and 30.1 kJ/mol).
•
Although PPBPI-CRs had different crosslinking densities of alkynyl groups, they
exhibited similar BET surface areas due to steric hindrance.