Conjugated microporous polymers with azide groups: A new strategy for postsynthetic fluoride functionalization and effectively enhanced CO2 adsorption properties

Article abstract of DOI:10.1039/c7cc06528k

A series of conjugated microporous polymers (CMPs) have been synthesized based on zinc-porphyrin building blocks. Azide groups incorporated within the pores of the CMPs were subjected to alkyne click conditions via a facile, one-step quantitative procedure, the resultant porous frameworks exhibited enhanced CO₂ sorption properties.

Full text of DOI:10.1039/c7cc06528k

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Conjugated microporous polymers with the azide groups: A new
strategy for postsynthetic fluoride functionalization en route for
enhanced CO2 adsorption properties
Received 00th January 20xx,
Accepted 00th January 20xx
Di Cui,a Chan Yaoa and Yanhong Xu*a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
A series of conjugated microporous polymers (CMPs) has been fluorescent sensors.10 Since Cooper and co-workers reported
synthesized based on zinc-porphyrin building block. Azide groups the first CMPs in 2007,11 over the past 10 years, more than
incorporated within the pores of the CMPs were subjected to hundreds CMPs have been constructed. In contrast with
alkyne click condition via
a facile, one-step quantitative metal-organic frameworks (MOFs) and zeolites, a distinct
procedure, the resultant porous frameworks exhibited enhanced feature of CMPs is that they have π-conjugation and
CO2 sorption properties.
permanent pores. In particular, CMPs based on
metalloporphyrin building blocks not only are prone to be
functionalized, but also have excellent thermal stability, which
is ascribed to the hybrid properties of metalloporphyrin
segments.12 Furthermore, some activated sites of the
metalloporphyrin, such as nitrogen atoms and built-in
unsaturated metal sites, resulting in the metalloporphyrin-
based CMPs can be an outstanding gas adsorption candidate.13
However, in spite of the great progress achieved so far, the
construction of CMPs that hold high performance in CO2
capture at low pressure and humid condition still faces great
challenges.
We face currently one of the greatest global problems is a
rapid rise of CO2 in the atmosphere due to anthropogenic
activities. In the future, the situation could become worse
because population expansion and industrial development will
produce a continuous increase of carbon dioxide emissions
after the combustion of carbon based energy resources.1 It is a
still challenging to develop effective techniques or strategies
that can effectively capture CO2 and alleviate the dilemma.
Carbon capture and sequestration (CCS) technology has been
proposed to solve this problem, which will play an important
role in meeting the huge demand for social development.2 In
CCS technology, new materials can capture CO2 with low-cost,
efficient and durable manner is the breakthrough core of the
success of CCS.3
CMPs are quite promising porous materials due to their high
porosity as well as high tunability of their pore surface functionality,
which is important in enhancing interactions with CO2. Given the
highly modular nature of CMPs, the introduction of chemical
functionality should be straightforward. Previous studies
reported that surface modification of porous materials with
polar groups, such as -COOH,14a -NO2,14b -SO3H,14c -OH,14d
arylamines,14e and heterocyclic nitrogen atoms,14f which can
significantly improve binding energy of CO2 because of the
high quadrupole momentand polarizability of CO2, thereby
increasing CO2 uptake and/or CO2 selectivity. It is well known
that perfluorinated alkanes are known to be more
hydrophobic than the corresponding hydrocarbons, so they
can be tolerant to water and remain their excellent capture
performance in the moisture condition, which is desirable in
practical applications.15a More interestingly, the high
electronegativity of fluoride would further promote CO2
adsorption through electrostatic interactions.15b Recently,
although MOF materials have emerged to show remarkable
CO2-uptake capacities, however, they are often very unstable
toward moisture.
Conjugated microporous polymers (CMPs) are a class of porous
organic materials, possessing π-conjugation, a fine control of
nanopores, and high chemical and thermal stability.4 These
merits of CMPs coupled with structural diversity, high
mechanical robustness, and high surface areas make it an
attractive platform for designing functional materials and have
shown outstanding performance in various fields, including gas
adsorption,5 light emitters,6 light-harvesting antennae,7
heterogeneous catalyst,8 supercapacitive energy storage,9 and
Consider above aspects, herein, we report access to fluoride
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50%N3-CMPs, (d) ZnP-75%N3-CMPs, (e) ZnP-100%N3-CMPs, (f) ZnP-5%F-
CMPs, (g) ZnP-25%F-CMPs, and (h) ZnP-50%F-CMPs, respectively.
functionalized CMPs using a novel one-step fluoride "clicking
post-synthetic modification procedure", performed under
Fig.
2 Nitrogen adsorption (filled circle) and desorption (open circle)
isotherm profiles of (a) ZnP-XN3-CMPs (X= 5, 25, 50, 75 and 100%) measured
at 77 k. Pore size distribution profiles of (b) ZnP-XN3-CMPs (X= 5, 25, 50, 75
and 100%).
Scheme 1. Schematic representation of (a) ZnP-XN3-CMPs (X = 5, 25, 50, 75
and 100%), (b) ZnP-XF-CMPs (X = 5, 25 and 50%).
Elemental analysis confirmed that the weight percentages of
C, H, and N contents were close to the theoretical values of
their infinite 2D polymers. In the FT-IR spectra, a strong -N3
stretch can be observed at about 2160 cm-1 in the ZnP-XN3-
CMPs (X = 5, 25, 50, 75 and 100%) (Fig. S1 and Fig. S2, ESI†),
and the intensities of the bands increased with increasing
azide contents, indicating the successful integration of azide
units at different contents in the pores of ZnP-XN3-CMPs (X = 5,
25, 50, 75 and 100%). After the click reaction, the
disappearance of the vibration bands at around 2120 cm-1,
implying that all the -N3 units in the CMPs are clicked to bear
the reactive sites (Fig. S2, ESI†). However, IR stretches from
unreacted azide groups could still be observed at about 2114
cm-1 in ZnP-75%N3-CMPs and ZnP-100%N3-CMPs, suggesting
that the azide–alkyne coupling is incomplete. Field-emission
scanning electron microscopy (FE-SEM) displayed that the
relatively mild synthetic condition (Scheme 1). The fluoride
contents in the CMP skeletons can be tunable by controlling
the percent of azide groups. We demonstrated this strategy by
controlling integration of fluoride sites into the pore to
synthesize CMPs containing different percentages of fluoride
that exhibited enhanced capture capacity in adsorption. ZnP-
XN3-CMPs (X = 5, 25, 50, 75 and 100%) were synthesized by the
Suzuki-coupling reacꢀon (ESI†). A three-component reaction
system
consisting
of
5,10,15,20-tetrakis(4-
tetraphenylbromo)zinc porphyrin as the core and a mixture of
4,4′-biphenyldiboronic acid (A) and (2,5-bis(azidomethyl)-1,4-
phenylene)diboronic acid (B) at varying molar ratios (X =
[B]/([A] + [B])×100 = 5, 25, 50, 75 and 100%) as the linkage
units were developed to construct the fluoride functionalized- original ZnP-XN3-CMPs (X = 5 and 25%) adopt ribbon-like shape
with the size of 10-100 nm (Fig. 1a and 1b). Interestingly, ZnP-
XN3-CMPs (X = 50, 75 and 100%) adopt spherical shape, and
the size increased along with increase of azide contents in the
skeletons (Fig. 1c-1e). In addition, the clicking ZnP-XF-CMPs (X
= 5, 25 and 50%) adopt also spherical shape with the size of
200-300 nm (Fig. 1f-h). High-resolution transmission electron
microscopy (HR-TEM) revealed ZnP-XN3-CMPs (X = 5, 25, 50, 75
and 100%) and ZnP-XF-CMPs (X = 5, 25 and 50%) displayed the
homogeneous distribution of nanometer-scale pores in the
textures (Fig. S3, ESI†). X-ray diffraction profiles also showed
that ZnP-XN3-CMPs (X = 5, 25, 50, 75 and 100%) and ZnP-XF-
CMPs (X = 5, 25 and 50%) are amorphous (Fig. S4, ESI†). And
ZnP-XN3-CMPs (X = 5, 25, 50, 75 and 100%) are stable up to
220 °C as revealed by thermal gravimetric analysis (Fig. S5, ESI†).
Furthermore, X-ray photoelectron spectroscopy (XPS) results
displayed fluoride element still existed in ZnP-XF-CMPs (X = 5,
25 and 50%) after clicking, and the peak intensity increased with
the fluoride content increased (ESI, Fig.S6). UV-vis spectra of the
CMPs, by allowing the integration of azide units of varying
contents into the edges (Scheme 1, [ZnP-XN3-CMPs, X = 5, 25,
50, 75 and 100%). Fluoride functionalized-CMPs were
synthesized via a mild one-step copper-catalyzed alkyne–azide
coupling reaction. In a typical experiment, ZnP-XN3-CMPs (X =
5, 25, 50, 75 and 100%) is soaked in DMF at 50 °C for three
days to obtain ZnP-XF-CMPs (X = 5, 25, 50, 75 and 100%),
respectively (see ESI†).
CMPs networks were recorded in the solid state (ESI, Fig. S7)
.
Fig. 1 FE-SEM images of (a) ZnP-5%N3-CMPs, (b) ZnP-25%N3-CMPs, (c) ZnP-
ZnP-XN3-CMPs (X = 5, 25 and 50%) polymers showed a broad
2 | J. Name., 2012, 00, 1-3
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cm3 g-1 (Table S2, ESI†). These results demonstrated the azide
groups really affect the pore diameters when we tuned the
azide content in the pores of CMPs skeletons.
absorption across the wavelength range 300-800 nm, however,
the polymer networks ZnP-XF-CMPs (X = 5, 25 and 50%)
exhibited a little bathochromic shift of around 5-42 nm (Fig. S7).
These results indicated clearly that the electronic states of the
CMPs systems can be adjusted and tuned by increasing the
Given that the CMPs have tuned functional azide groups
pointing into the pores, we were naturally interested in
evaluating their absorbent potential. First, we investigated the
effect of the azide content on the CO2 adsorption behaviors of
ZnP-XN3-CMPs (X= 5, 25, 50, 75 and 100%) at 298 K and 1.0 bar
(Fig. 3a and Table S1). Interestingly, we observed an increased
trend in the adsorption of CO2 with the raise of azide contents
in the skeletons. For instance, ZnP-5%N3-CMPs at 298 K and
1.0 bar exhibited a capacity of 26 mg g-1 (blue circle), ZnP-
25%N3-CMPs (green circle) and ZnP-50%N3-CMPs (red circle)
displayed capacities 31 and 49 of mg g-1, respectively. However,
the CO2 capacity of CMPs showed a decrease trend when the
azide content is higher than 75%, such as ZnP-75%N3-CMPs
(cyanl circle) and ZnP-100%N3-CMPs (gray circle) exhibited the
CO2 uptake of 43 and 40 mg g-1. It is reasonable to assume that
this remarkable enhancement of CO2 adsorption capacity is
due to the pore size of CMPs more suitable for CO2 adsorption
with the increase of azide contents in the pores. At 273 K, the
capacity of CO2 is 44, 54, 87, 72 and 69 for mg g-1 for ZnP-
5%N3-CMPs, ZnP-25%N3-CMPs, ZnP-50%N3-CMPs, ZnP-75%N3-
CMPs and ZnP-100%N3-CMPs, respectively (Fig. 3b and Table
S1). The result suggested that the pore properties (pore size,
surface area and pore volume) of CMPs could be finely tuned
by introducing proper edge units to porous polymer networks.
fluoride contents
.
Porous structures were investigated by nitrogen sorption
isotherm measurements at 77 K. In light of IUPAC classification,
ZnP-XN3-CMPs (X= 5, 25 and 50%) exhibit a combination of types I
and IV; the other two polymers (ZnP-XN3-CMPs (X= 75 and 100%))
show type I isotherm curves (Fig. 2a). From all isotherms, we
can see all the networks show an evident hysteresis loop,
which is partly attributed to the swelling in a flexible polymer
network, as well as mesopore contribution.16 The presence
and magnitude of this hysteresis may be an indication of the
softness of the materials. Moreover, a sharp rise in the high
pressure region (P/P0 > 0.8) is also observed in the sorption
isotherms of ZnP-XN3-CMPs (X= 5, 25 and 50%), respectively,
suggesting that the three materials possess some macropores,
which is attributed to the nitrogen condensation in
interparticular voids formed by the aggregation of polymer
microspheres, which is similar to the previous reports.16
Surprisingly, the Brunauer–Emmett–Teller (BET) surface areas
of CMPs decreased along with increasing amount of azide
groups in the reaction system. For example, the BET surface
areas of ZnP-5%N3-CMPs, ZnP-25%N3-CMPs, ZnP-50%N3-CMPs,
ZnP-75%N3-CMPs and ZnP-100%N3-CMPs are 711, 685, 654,
565 and 477 m2 g-1, and their corresponding pore volumes are
0.7659, 0.7029, 0.6812, 0.4383, and 0.3446 cm3 g-1,
respecꢀvely (Table S1, ESI†). Pore size distributions were
calculated by the Saito-Foley (SF) method, which revealed pore
sizes centered at 0.6-1.5 nm (Fig. 2b), and main pores
exhibited a decrease trend with the increasing azide content in
the pores (Fig. 2b). After the click reaction, the BET surface
areas of fluoride functionalized-CMPs are 430, 362, 240, 148,
and 37 m2 g-1 for ZnP-5%F-CMPs, ZnP-25%F-CMPs, ZnP-50%F-
CMPs, ZnP-75%F-CMPs, and ZnP-100%F-CMPs, respectively
(Fig. S8, Table S1, ESI†). The pore volumes are 0.6767, 0.5211,
0.3762, 0.1790 and 0.1187 cm3 g-1 for ZnP-5%F-CMPs, ZnP-
25%F-CMPs, ZnP-50%F-CMPs, ZnP-75%F-CMPs, and ZnP-
100%F-CMPs, respectively.
In order to clarify whether the azide groups affect the BET
surface areas and pore volumes in the CMPs skeletons. We
synthesized a series of CMPs (ZnP-XC-CMPs (X = 5, 25, 50, 75
and 100%, C= benzene-1,4-diboronic acid) without azide
groups under the same reaction condition (Scheme S1, ESI†). A
three-component reaction system consisting of 5,10,15,20-
tetrakis(4-tetraphenylbromo)zinc porphyrin as the core and a
mixture of 4,4′-biphenyldiboronic acid (A) and benzene-1,4-
diboronic acid (C) at varying molar ratios (X = [C]/([A] +
[C])×100 = 5, 25, 50, 75 and 100%) as the linkage units were
developed to construct the CMPs (ZnP-XC-CMPs (X = 5, 25, 50,
Fig. 3 CO2 adsorption isotherms. (a) ZnP-XN3-CMPs (X= 5, 25, 50, 75 and
100%) at 298 K and 1.0 bar; (b) ZnP-XN3-CMPs (X= 5, 25, 50, 75 and
100%) at 273 K and 1.0 bar; (c) ZnP-XF-CMPs (X= 5, 25 and 50%) at 273
K and 1.0 bar; (d) the isosteric heat of CO2 adsorption
.
75 and 100%)). These CMPs also exhibited type I and IV
isotherm curves, which are similar to those of ZnP-XN3-CMPs
(X= 5, 25 and 50%) (Fig. S9 and Table S2, ESI†). However, they
showed very similar BET surface areas of 430-483 m2 g-1, main
pore sizes of 0.70-0.85 nm and pore volumes of 0.4675-0.5333
Then we investigated the capacity of CO2 in the ZnP-XF-
CMPs (X= 5, 25 and 50%). In contrast to original CMPs, the
uptake of ZnP-XF-CMPs (X= 5, 25 and 50%) displayed an
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1
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and 1.0 bar exhibited a capacity of 34 mg g-1, which was 1.31-
times of that of the original CMPs (ZnP-5%N3-CMPs) (Fig. S10a,
ESI†). The CO2 uptake of ZnP-25%F-CMPs and ZnP-50%F-CMPs
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and 1.84-times as high as original CMPs (ZnP-25%N3-CMPs and
ZnP-50%N3-CMPs) (Fig. S10(b-d), ESI†). Then, we measured the
CO2 capacity of the CMPs from 298 K to 273 K to further
investigate ultra-micropores in CMPs and to examine their
potential application in post-combustion CO2 capture. ZnP-
5%F-CMPs, ZnP-25%F-CMPs and ZnP-50%F-CMPs displayed the
CO2 capacity of 58, 84 and 130 mg g-1 at 273 K and 1.0 bar,
respectively (Fig. 3c and Fig. S10(b-d)). The CO2 capture
capacity of ZnP-XF-CMPs (X= 5, 25 and 50%) is 1.31-, 1.56- and
1.49-times of that of ZnP-XN3-CMPs (X= 5, 25 and 50%) at the
same conditions, respectively. These results indicated that the
increase of fluoride contents in the skeletons could effectively
improve the CO2 adsorption capacity of the polymers at the
same conditions.
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To investigate the binding affinity of the studied CMPs
towards CO2, we calculated the isosteric heats of adsorption
from Clausius–Clapeyron equation using adsorption data
collected at 273 K and 298 K. ZnP-XF-CMPs (X = 5, 25 and 50%)
had relatively higher CO2 uptake among the synthesized CMPs
with the heat of adsorption of about 32-37 kJ mol-1 (Fig. 3d).
The Qst values for ZnP-XN3-CMPs (X = 5, 25, 50, 75 and 100%)
are about 18-25 kJ mol-1, which are lower than those of their
corresponding perfluoroalkyl counterparts (Fig. S11, ESI†). The
result suggested that introducing fluoride element in the
polymers can effectively enhance the adsorption enthalpy of
the porous materials.
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In summary, a new strategy for construction of porous
polymer with CMPs architectures has been developed.
Implementation of the strategy leads to the successful
development of three novel fluoride functionalized-CMPs,
which exhibit highly efficient uptake of CO2 than those of
original CMPs (ZnP-XN3-CMPs (X = 5, 25 and 50%)) at the same
conditions. Moreover, all of the fluoride functionalized-CMPs
show high isosteric heats of CO2 adsorption (32-37 kJ mol-1).
This work not only indicates that highly complicated three-
dimensional polymeric structures can be facilely constructed
from simple building blocks but also suggests a promising way
to improve the isosteric heats and CO2 uptake of porous
materials. This provides a new idea for the development of
new strategies for the construction of porous organic materials
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The financial support of the National Natural Science
Foundation of China (Grants no. 21501065), Science and
Technology Program of Jilin Province (Grants no. 20160101319JC),
Changbai Mountain Scholars Program (Grants no. 2013073), and
Research on the Science and Technology of Education Department
of Jilin Province (Grants no. 2016220) is acknowledged.
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Notes and references
4 | J. Name., 2012, 00, 1-3
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Conjugated microporous polymers with the azide groups: A new
strategy for postsynthetic fluorine functionalization en route for
enhanced CO2 adsorption properties
Di Cui,a Chan Yaoa and Yan-hong Xu*a,b
Corresponding Author:
Professor Yan-Hong Xu
aKey Laboratory of Preparation and Applications of Environmental Friendly
Materials (Jilin Normal University), Ministry of Education, Changchun, 130103,
China
bKey Laboratory of Functional Materials Physics and Chemistry of the Ministry of
Education, Jilin Normal University, Siping 136000, China
The different azide group contents incorporated within the pore of the
zinc-porphyrin CMPs were subjected to alkyne click condition via a facile, one-step
quantitative procedure, the route can effectively enhance the CO2 sorption and the
adsorption enthalpy of porous materials.

ChemComm
Page 6 of 6
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DOI: 10.1039/C7CC06528K