Facile preparation of dibenzoheterocycle-functional nanoporous polymeric networks with high gas uptake capacities7

Article abstract of DOI:10.1021/ma500080s

A consolidated ionothermal strategy was developed for the polymerization of thermally unstable nitriles to construct high performance materials with permanent porosity, and carbazole, dibenzofuran, and dibenzothiophene were separately introduced into covalent triazine-based networks to investigate the effects of heterocycles on the gas adsorption performance. Three nitriles, namely 3,6-dicyanocarbazole, 3,6-dicyanodibenzofuran, and 3,6- dicyanodibenzothiophene, were designed and synthesized, which were readily converted to heat-resistant intermediates at a moderate temperature and then polymerized to create highly porous poly(triazine) networks instead of the traditional one-step procedure. This documents an improved strategy for the successful construction of heterocyclic-functional triazine-based materials. The chemical structures of monomers and polymers were confirmed by ¹H NMR, FTIR, and elemental analysis. Such polymers with high physical-chemical stability and comparable BET surface areas can uptake 1.44 wt % H₂ at 77 K/1 bar and 14.0 wt % CO₂ at 273 K/1 bar and present a high selectivity for gas adsorption of CO₂ (CO₂/N₂ ideal selectivity up to 45 at 273K/1.0 bar). The nitrogen- and oxygen-rich characteristics of carbazole and dibenzofuran feature the networks strong affinity for CO₂ and thereby high CO₂ adsorption capacity. This also helps to thoroughly understand the influence of pore structure and chemical composition on the adsorption properties of small gas molecules.

Full text of DOI:10.1021/ma500080s

Article
pubs.acs.org/Macromolecules
Facile Preparation of Dibenzoheterocycle-Functional Nanoporous
Polymeric Networks with High Gas Uptake Capacities
†
†
,†
‡
,†
§
§
Shaofei Wu, Yao Liu, Guipeng Yu,* Jianguo Guan, Chunyue Pan,* Yong Du, Xiang Xiong,
,
∥
and Zhonggang Wang*
†
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
‡
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan
4
30070, China
§
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China
State Key Laboratory of Fine Chemicals, Department of Polymer Science & Materials, Dalian University of Technology, Dalian
∥
1
16012, China
*
S Supporting Information
ABSTRACT: A consolidated ionothermal strategy was
developed for the polymerization of thermally unstable nitriles
to construct high performance materials with permanent
porosity, and carbazole, dibenzofuran, and dibenzothiophene
were separately introduced into covalent triazine-based
networks to investigate the effects of heterocycles on the gas
adsorption performance. Three nitriles, namely 3,6-dicyano-
carbazole, 3,6-dicyanodibenzofuran, and 3,6-dicyanodibenzo-
thiophene, were designed and synthesized, which were readily
converted to heat-resistant intermediates at a moderate
temperature and then polymerized to create highly porous
poly(triazine) networks instead of the traditional one-step
procedure. This documents an improved strategy for the successful construction of heterocyclic-functional triazine-based
1
materials. The chemical structures of monomers and polymers were confirmed by H NMR, FTIR, and elemental analysis. Such
polymers with high physical−chemical stability and comparable BET surface areas can uptake 1.44 wt % H at 77 K/1 bar and
2
1
2
4.0 wt % CO at 273 K/1 bar and present a high selectivity for gas adsorption of CO (CO /N ideal selectivity up to 45 at
73K/1.0 bar). The nitrogen- and oxygen-rich characteristics of carbazole and dibenzofuran feature the networks strong affinity
2
2
2
2
for CO and thereby high CO adsorption capacity. This also helps to thoroughly understand the influence of pore structure and
2
2
chemical composition on the adsorption properties of small gas molecules.
INTRODUCTION
covalent bonds. High stability (thermal and chemical), low
skeletal density, and multitudinous structural modification
■
One of the most urgent challenges facing energy sector is the
mitigation of greenhouse gases implicated in global warming.
Although some technologies including amine scrubbing and
cryogenic separation are already available for CO capture, the
1
methods enable POPs to be promising candidates for CO
sorbents. Major research efforts are currently focused on a
2
7
rational design of POPs to combine the CO -sorption capacity
2
2
and selectivity as well as good reversibility of POPs under
substantial energy consumptions required for CO release for
2
8
ambient conditions. Two factors should be taken into account
sequestration and regeneration of the amine solutions togethe2r
for a high performance CO sorbent. First, narrow ultra-
2
with severe corrosion of equipment limit their popularity.
micropores (<1 nm) make a greater contribution to CO2
Adsorption by porous solids (such as zeolite, metal−organic
frameworks, etc.), featuring large capacity and low cost, was
deemed as the promising and competitive method for CO2
adsorption than wide micropores and mesopores, considering
9
thermodynamic size of CO , which can be ascribed to the fact
2
8c,10
3
that the former enhances the filling by the CO molecule.
recovery. However, the main drawback of such cation-
2
Second, the acceptable binding energy between host and guest
CO2 molecule would enable the strong but reversible
containing sorbents is their low tolerance to water vapor that is
usually present in the gas stream. The water molecules with
dipole moments will preferentially interact with the cations, thus
significantly damaging the popularity of such CO sorbents.
4
11
adsorption−desorption. For the second concern, one of the
5
2
Recently, a new type of substitute for traditional porous
sorbents, namely porous organic polymers (POPs), has been
constructed from various pure organic building blocks via robust
Received: January 10, 2014
Revised: April 27, 2014
Published: May 2, 2014
6
©
2014 American Chemical Society
2875
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Article
most extensively studied and effective strategies is the
introduction of polar functional moieties onto the pore surface
either through the preoptimization of building blocks or using
influence of dibenzoheterocyclic units on the selective CO2
adsorption for the first time.
12
postmodification method. Typically, the network A disclosed
EXPERIMENTAL SECTION
■
(
by Cooper et al., which is composed of neat benzene rings, can
Materials. Dibenzofuran, dibenzothiophene, carbazole, and copper-
I) cyanide were purchased from Aladdin Chemical Inc. and used as
−1
uptake CO of 2.65 mmol g at 273 K and 1 bar, while triazole-
2
functional network C exhibits a remarkably improved CO
2
received. Zinc chloride was refluxed and distilled over thionyl chloride to
remove water, and then excess thionyl chloride was azeotropically
distilled with toluene. After the removal of thionyl chloride and toluene,
anhydrous zinc chloride was obtained after being dried at 180 °C under
vacuum for 24 h. Unless otherwise specified, all other solvents and
reagents were purchased from Energy Inc. and used as received.
Characterization Methods. FT-IR spectra were collected with a
VARIAN 1000 FT-IR (scimitar series) spectrometer in the 400−4000
−1
13
uptake capability (3.86 mmol g ). Han et al. constructed
microporous polycarbazole (COP-1) with a high uptake capacity
for CO (21.2 wt %) and a moderate CO /N adsorption
2
2
2
1
4
selectivity (25). Exciting CO capture performance close to
2
those required for either pre- or postcombustion capture is also
1
5
demonstrated by polyamine and sulfonate-grafted PPN-6s,
16
oxygen-rich phloroglucinol-based porous polymers, nitrogen-
−1
cm region (KBr pressed disks). Thermogravimetric analysis (TGA)
7a,17
rich microporous polybenzimidazoles,
nitrogen- and oxygen-
was performed at a heating rate of 10 K/min under N or air atmosphere
2
18
1
rich microporous cyanate resins, etc. As common commercially
available materials, carbazole, dibenzothiophene, and dibenzo-
furan are suitable blocks for building porous organic polymers
due to their unique electroactivity and useful photophysical
property. In these cases, the introduction of dibenzoheterocycles
makes the polymer electron-rich, and hence this approach
appears promising in improving isosteric heat of adsorption and
gas adsorption capability. In addition, each of the dibenzohetero-
cycles contains two phenyl rings but connected by a different
heterocyclic core. Thus, after cross-linking, the polar surface in
the networks could be systematically varied while same
topologies will be obtained because of similar initial structure,
which enables us to examine the influence of pore structure and
chemical composition on the adsorption capacity and selectivity
toward small gas molecules.
using a PerkinElmer TGA 7. H NMR (400 MHz) spectra were
obtained with a Bruker spectrometer at an operating temperature of 25
°
C using DMSO-d or CDCl as solvents, and the data were listed in
6 3
1
3
parts per million downfield from tetramethylsilane (TMS). C NMR
100 MHz) spectra were obtained with a Bruker spectrometer at an
(
operating temperature of 25 °C. CHN analysis was performed on a
Vario ELIII CHNOS Elementaranalysator from Elementaranalysesy-
teme GmbH. Wide-angle powder X-ray diffraction (WAPXRD) data
were collected over the 2θ range 5°−60° on a CPS120 Inel
diffractometer equipped with Ni-filtered Cu Kα radiation (40 kV, 100
−1
mA) at room temperature with a scan speed of 5° min . High-
resolution transmission electron microscopy (HR-TEM) images were
collected in a JEOL JEM-2100F microscope at an accelerating voltage of
2
00 kV. Prior to TEM measurement, the sample was ultrasonically
dispersed in ethanol and dropped onto a copper grid coated with a
carbon film. Scanning electron microscopy (SEM) experiments were
performed on a FEI Quanta-200 scanning electron microscope. The dry
state polymer surface areas and pore size distributions were performed at
a Micromeritics ASAP 2020 sorption analyzer by nitrogen adsorption
and desorption at 77 K. The specific surface areas (BET) were calculated
As a special and emerging class of POPs, covalent triazine-
based frameworks (CTFs) were first developed utilizing dynamic
trimerization reaction in ZnCl ionothermal conditions by Kuhn
2
according to the BET model in the relative pressure (P/P ) ranging from
et al. Although only CTF-1 shows same interesting crystalline
properties as COF-1, a new cheap method to obtain porous
CTFs from abundant, thermally stable organic nitriles was
0
0
.01 to 0.1. Pore size distributions were derived from the N adsorption
2
isotherms using the NLDFT (nonlocal density functional theory)
method. CO adsorption isotherms were measured at 273 and 298 K up
1
9
2
developed. However, much harsher reaction conditions
reaction temperatures >400 °C) have to be applied to enable
to 1.0 bar, while H adsorption isotherms were measured at 77 and 87 K
2
(
with the same pressure scale. High-purity gas (99.999%) was used for
adsorption experiments. Prior to the measurements, the samples were
degassed at 200 °C under high vacuum for 12 h.
Synthesis of Monomers. 3,6-Dibromocarbazole. A 500 mL
round-bottomed flask was charged with carbazole (8.4 g, 50 mmol) and
20
the reversible formation of triazines. This completely destroys
the polymerization feasibility of a large number of building blocks
with heterocyclic moieties (e.g., carbazole and thiophene) that
are easily broken down but deliver a great positive effect to gas
adsorption ability. Impressive technologies such as the micro-
wave-assisted method by Qiu and Cooper and acid catalysis by
Liu known as high efficiency, however, do not fundamentally
chloroform (300 mL), and a solution of Br (5.15 mL, 105 mmol) in 50
2
mL of chloroform was added at 0 °C drop by drop. The mixture was
stirred at 0 °C for another 1 h and then transferred to room temperature
for another 12 h. The resultant mixture was poured into 1000 mL of
sodium bicarbonate solution (1 mol/L), and the organic phase was
separated off and dried over anhydrous sodium sulfate. The volume of
the solution was reduced by rotary vaporization. After recrystallization
2
1
hamper the thermal decomposition and acidolysis. Aromatic
nitriles can cyclotrimerize to thermally stable phenyl-s-triazine
derivatives with the aid of acid at moderate temperatures. The
basis of this outstanding work goes back to several contributions
by Marvel and Huang which described the instantaneous
formation of polytriazine oligomers of low polymerization
by ethanol, a crystalline pale red solid (13.3 g) was obtained. Yield: 82%;
1
mp: 204−206 °C. H NMR (CDCl ): 8.07−8.11 (s, 2H), 7.48−7.56 (d,
3
2
H), 7.24−7.32 (d, 2H).
,6-Dicyanocarbazole. 3,6-Dibromocarbazole (6.5 g, 20 mmol) and
3
22
degree under the catalysis of ZnCl2. This has initiated our
efforts to develop a flexible strategy to construct high
performance networks with permanent porosity from such
nitrile blocks.
cuprous cyanide (8.89 g, 100 mmol) were charged, and then 250 mL of
dry DMF was injected by syringe under an N atmosphere. After being
2
stirred at 150 °C for 48 h, the reaction mixture was poured into a cold
solution of 100 g of ferric chloride in 150 mL of concentrated
hydrochloric acid and stirred for another 2 h. The brown solid was
collected by filtration, washed with water and ethanol several times, and
dried under vacuum. The obtained crude product was chromatographed
on a silica gel column with petroleum ether/dichloromethane as eluent,
Inspired by these works, a consolidated ionothermal strategy
(instead of traditional one-step procedure) for the building of
functional CTFs from three temperature-unstable monomers
was demonstrated. We introduce carbazole, an extensively
employed moiety, and two uninvestigated units, namely
dibenzofuran and dibenzothiophene, into covalent triazine-
based frameworks. Our study also aims to demonstrate the
1
and a white solid (1.5 g) was obtained. Yield: 35%. H NMR (DMSO):
8
.16−8.18 (s, 2H), 7.72−7.78 (d, 2H), 7.64−7.7 (d, 2H).
3,6-Dibromodibenzofuran. The synthesis procedure of 3,6-
dibromodibenzofuran was almost the same as for 3,6-dibromocarbazole.
2
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The product was obtained as a white solid. Yield: 89%; mp: 226−227
Notably, all monomers motioned above are thermally stable to
endure continuous heating at 400 °C or even at other higher
temperatures (600 °C). To probe this feasibility, TGA
measurements (Figure S1, Supporting Information) on the
three monomers were conducted prior to the polymerization.
1
°
C. H NMR (CDCl ): 8.0−8.04 (s, 2H), 7.55−7.59 (d, 2H), 7.42−7.46
3
(
d, 2H).
3
,6-Dicyanodibenzofuran. 3,6-Dicyanodibenzofuran was prepared
in almost the same procedure as for 3,6-dicyanocarbazole. The product
1
was obtained as a pale yellow solid. Yield: 39%. H NMR (CDCl ):
3
The highest decomposition temperature (T , recorded as the
8
.31−8.35 (s, 2H), 7.84−7.86 (d, 2H), 7.74−7.78 (d, 2H).
d
temperature for 10 wt % mass loss under N atmosphere) was
3
,6-Dibromodibenzothiophene. 3,6-Dibromodibenzothiophene
2
was prepared in almost the same procedure as for 3,6-dibromocarbazole.
recorded at 350 °C by 3,6-dicyanodibenzofuran, while those of
the others (3,6-dicyanodibenzothiophene: Td = 250; 3,6-
The product was obtained as a white solid. Yield: 79%; mp: 225−227
1
°
C. H NMR (CDCl ): 8.23−8.25 (s, 2H), 7.69−7.74 (d, 2H), 7.56−7.6
dicyanocarbazole: T = 252 °C) are much lower relative to
3
d
(
d, 2H).
previous disclosed building blocks such as o-DCB, DCBP, and
3
,6-Dicyanodibenzothiophene. 3,6-Dicyanodibenzothiophene was
19
NDC (T > 400 °C). Additionally, our results demonstrated
d
prepared in almost the same procedure as for 3,6-dicyanodibenzofuran.
that the traditional synthetic technology by which the monomer
was heated to 400 °C by one step leads to almost complete
carbonization, while that using trifluoromethanesulfonic acid as
catalyst under room temperature has caused breakage within C−
N and C−O linkages of the nitrile monomers (Table S1,
Supporting Information). This definitely hampers the facile
construction of high performance porous materials and their
wide applications as small gas sorbents.
1
The product was obtained as a pale yellow solid. Yield: 31%. H NMR
(
CDCl ): 8.48−8.5 (s, 2H), σ = 8−8.04 (d, 2H), σ = 7.78−7.82 (d, 2H).
3
Synthesis of NPTNs. NPTN-1a. NPTN-1a was synthesized by
heating a mixture of 3,6-dicyanocarbazole (0.3 g, 1.4 mmol) and ZnCl2
(
1.84 g, 14 mmol) in a quartz tube (3 × 5 cm) according to the
7c,23
literature.
The tube was evacuated to a high vacuum and then sealed
rapidly. Following by a temperature program (250 °C/10 h), the quartz
tube was cooled to room temperature, and the reaction mixture was
subsequently ground and then washed thoroughly with water to remove
the catalyst. A yellow solid was obtained. Yield: 99%.
NPTN-1b. The synthesis procedure of NPTN-1b was similar to that
for NPTN-1a, except a different temperature program (250 °C/10 h,
For comparison, different heating cycles were applied to the
polymerization of the carbazole-functional nitriles. The specific
synthetic results were displayed in Table S1. As described,
heating at reaction temperatures of less than 350 °C mainly
yielded deep yellow or brown organosoluble products (NPTN-
1a,b,c) which are supposed to be low-molecular-weight
compounds. By one-step heating the monomer 3,6-dicyanocar-
bazole to 400 °C in the traditional procedure a black insoluble
material (NPTN-1d) was obtained. As expected, only networks
with high degree of carbonation were obtained, accompanying
with the extremely low yield (62%) and high nitrogen loss as
shown by element analysis (Table S2). Fourier infrared spectrum
analysis was chosen to probe the deeper structure variations of
the materials. NPTN-1a displays almost the same features to the
initial monomers implying a low-level trimerization. As shown in
Figure S2, the expected intermediates were generated after
heating at around 300 °C (NPTN-1b). Typically, after
polymerization at 300 °C, the intensity of nitrile absorption at
3
00 °C/10 h) was applied during the heating cycles. A brown solid was
obtained. Yield: 98%.
NPTN-1c. The synthesis procedure of NPTN-1c was similar to that
for NPTN-1a, except a different temperature program (250 °C/10 h,
3
00 °C/10 h, 350 °C/10 h) was applied during the heating cycles. A
black solid was obtained in a yield of 98%.
NPTN-1d. For the synthesis of NPTN-1d, a traditional synthetic
method in which the monomer was heated to 400 °C by one step was
utilized. Unfortunately, at the first time the reaction in a quartz tube (3 ×
5
cm) was suspended suddenly due to a blast of the tube after 10 h
heating program (supposing to be 40 h). The method was repeated
twice by changing the size of quartz tube (3 × 10 cm), and then a black
solid was obtained after removing the catalyst by water. Yield: 62%
(
2nd) and 64% (3rd).
NPTN-1. NPTN-1 was synthesized by heating a mixture of the
synthesized 3,6-dicyanocarbazole (0.3 g, 1.4 mmol) and ZnCl (1.84 g,
2
1
4 mmol) in a quartz tube (3 × 5 cm). The tube was evacuated to a high
vacuum and then sealed rapidly. Following by a temperature program
250 °C/10 h, 300 °C/10 h, 350 °C/10 h, 400 °C/20 h), the quartz tube
−1
about 2235 cm is about 39% of the origin intensity of 3,6-
dicyanocarbazole, while it is around 24% of the origin intensity
after curing at 350 °C (NPTN-1c), normalized to the C−H
stretch band at 3066 cm− (Figure S3). Additionally, a gradual
increase of absorption intensity at round 1360 and 1510 cm−
indicates a remarkably improved conversion with an increasing
reaction temperature. Thermogravimetric analysis (TGA) under
(
was cooled to room temperature, and the reaction mixture was
subsequently ground and then washed thoroughly with water to remove
most of the catalyst. Further stirring in diluted HCl for 15 h was carried
out to remove the residual salt. The resulting black powder was filtered
and washed successively with water and methyl alcohol, followed by an
overnight Soxhlet extraction using acetone, methyl alcohol, and hexane
as eluting solvent sequentially, and finally dried in vacuum at 150 °C.
Yield: 94%.
1
1
a N atmosphere displayed in Figure 1 demonstrates a superior
2
stability compared to the initial monomers. As depicted, after
NPTN-2. Synthesis procedure of NPTN-2 was almost the same as for
NPTN-1, and a black solid was obtained starting from 3,6-
dicyanodibenzofuran. Yield: 96%.
NPTN-3. Synthesis procedure of NPTN-3 was almost the same as for
NPTN-1, and a black solid was obtained starting from 3,6-
dibromodibenzothiophene. Yield: 93%.
RESULTS AND DISCUSSION
■
A series of covalent triazine-based frameworks (CTFs) were
obtained successfully from the abundant organic nitriles such as
o-DCB (1,2-dicyanobenzene), p-DCB, m-DCB, and 4,4′-
1
9,24
dicyanobiphenyl (DCBP) reported by Kuhn and Antonietti,
7c
1
,3,5-tricyanobenzene by Thomas, 2,6-naphthalenedicarboni-
25
trile (NDC) by Bojdys, supramolecule tetranitrile and (1,3-
bis-, 1,3,5-tris-), 1,3,5,7-tetrakis(4-cyanophenyl)adamantine by
27
Figure 1. TGA thermograms of 3,6-dicyanocarbazole and NPTN-1
under different heating cycles.
2
3,26
Janiak,
and 1,4-dicyano-2,3,5,6-tetrafluorobenzene by Han.
2
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Scheme 1. Synthesis Routes to NPTNs
polymerization at 300 °C, 10 wt % mass loss temperature of the
obtained network (NPTN-1b) has been promoted from 250 to
and dibenzoheterocyclic units. This physical and chemical
stability is higher than MOFs (unstable to heat), molecular
3
d,28
3
05 °C. With further heating at 350 °C, the T of the resultant
sieve (unstable to acid), and COFs, etc.,
and comparable to
d
29
1c,30
31
network (NPTN-1c) was raised to 350 °C. Black and highly
cross-linked polymers (NPTN-1) were obtained by heating
NPTN-1c at the temperature of 400 °C for another 20 h. In
addition to a higher yield (>90%) than NPTN-1d, we assume
that thermally unstable nitriles were readily converted to heat-
resistant intermediates as we expected, while the carbonation has
been suppressed effectively.
other POPs such as HCPs, CMPs,
the network application value under a harsh environment.
The chemical connectivity and the structure of NPTNs were
PIMs, etc., endowing
32
1
3
characterized by Fourier transform infrared (FT-IR), solid
C
CP/MAS NMR spectra. As illustrated in FT-IR spectra (Figures
S3−S5), the disappearance of intense CN band at about 2230
−1
cm is indicative of a high conversion of nitriles, while the
appearance of strong absorption bands at round 1360 (C−N)
and 1510 cm− (CN) and a signle peak at 173 ppm (C in s-
Herein, the novel series of nanoporous triazine-based
networks (NPTNs) functioned by dibenzoheterocyclic units
1
13
(i.e., carbazole, dibenzofuran, and dibenzothiophene) were
triazine) in the solid C NMR spectrum (Figure S6) suggests the
successful formation of triazine. The other major peaks observed
at 138 and 129 ppm could be assigned to the substituted aromatic
carbon bonded to nitrogen atom and substituted aromatic
carbon of aromatic ring connected with triazine ring,
synthesized from aromatic nitriles in sealed quartz ampules via
a modified dynamic reaction (Scheme 1). For the preparation of
NPTNs, a kind of stable intermediates can be synthesized in
molten ZnCl under moderate temperatures, prior to the
2
generation of the target product. Such intermediates, namely
prepolymers with low polymerization degrees (e.g., trimer,
pentamer), are not highly cross-linked but stable enough for high
reaction temperatures comparing to the initial monomers. The
low-molecular-weight compounds without any pore character-
istics can be easily resolved by the Lewis acid. When a higher
reaction temperature is used, highly cross-linked polymers will be
readily obtained in quantitative yields under ionothermal
conditions.
33
respectively. Morphologies study of NPTNs by SEM
demonstrates aggregates of uniform and compact microgel
particles with a size of 100−200 nm. A dark and bright area can be
clearly observed from HR-TEM images, confirming a porous
characteristic, while the intermediates NPTN-1c and NPTN-1d
present a dense and compact surface on the SEM/TEM images
implying nonporous nature. As shown in Figure S17, the
isotherm of NPTN-1c and NPTN-1d display almost no uptake
under low relative pressure (P/P < 0.2) and slight uptake up to
0
The obtained networks are insoluble in any common organic
solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylfor-
mamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-
pyrrolidone (NMP), and tetrahydrofuran (THF), along with
diluted HCl solution (10 wt %), implying a physical−chemical
stable hyper-cross-linked nature. The stability test was further
examined by refluxing NPTNs in diluted HCl solution (10 wt %)
for 5, 20, and 48 h, and neither color change nor weight loss was
observed. The recovered networks were evaluated after acid
soaking using nitrogen sorption experiments at 77 K. The
apparent surface area values calculated from Brunauer−
Emmett−Teller (BET) models are all kept comparing with the
original networks. It is worth mentioning that the nitrogen loss as
evidenced by the elemental analysis (EA in Table S2) is low,
P/P = 0.99, confirming nonporous nature. PXRD spectra of
NPTNs are featureless, suggesting their amorphous nature
0
(
Figure S18). Briefly, three hyper-cross-linked polymers with
good thermal and physical−chemical stability were constructed
from temperature-unstable nitriles by the step-by-step ionother-
mal method.
1
9,20
which is consistent with other studies.
TGA thermograms
under air condition deliver excellent thermostability of NPTNs
with 10 wt % weight loss at round 470 °C (Figure S2). The Td
values of NPTN-1−3 were raised by 220, 230, and 120 °C
compared with those of the corresponding monomers
determined under N atmosphere, respectively. The significantly
2
promoted stability is most possibly resulted from the strong
charge transfer interactions between the formed s-triazine rings
Figure 2. Nitrogen sorption isotherms of NPTNs at 77 K.
2
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The nitrogen adsorption isotherms exhibit a sharp uptake in
microporosity fraction (V /V ) was the least (47.3%, 46.3%, and
47% for NPTN-1, NPTN-2, and NPTN-3, respectively).
0.1
t
the low pressure region (P/P < 0.01), implying a significant
0
microporosity for the networks, whereas the isotherms also
demonstrate the presence of mesoporous for another relative
steady rise phase ranges from 0.2 to 0.8 (P/P0). All three
networks show significant increase of nitrogen uptake over 0.8
The CO adsorption isotherms at 273 and 298 K (Figure 4)
demonstrated that the absorbed amount continually increased
2
3
4
(
P/P ), suggesting the presence of macroporous structure. This
0
can be interpreted as the interparticulate voids arising from the
loose packing of small particles as observed in the SEM
micrographs. The desorption isotherms display a typical
desorption−adsorption hysteresis, which is ascribed to the
softness of organic polymer skeleton and swelling effect in critical
nitrogen.
BET surface area values calculated from relative pressure
between 0.01 and 0.1 were listed on Table 1. NPTN-2 shows the
Table 1. Pore Parameters for NPTNs
a
2
b
3
c
3
polymer
SABET (m /g) VTotal (cm /g) V0.1 (cm /g) V0.1/Vt
Figure 4. CO adsorption isotherms of NPTNs at 273 and 298 K.
2
NPTN-1
NPTN-2
NPTN-3
1187
1558
1055
0.93
1.23
0.83
0.44
0.57
0.39
47.3
46.3
47
with the rising pressure, implying that the adsorptions have not
reached their equilibrium or saturated state in the pressure range
investigated. Among the porous materials, dibenzofuran-func-
a
Calculated using adsorption branches over the pressure range 0.01−
.1 bar of N isotherm at 77 K. Determined from the N isotherm at
b
0
2
2
tional NPTN-2 exhibits the highest CO uptake of 14.0 wt % at
c
2
P/P = 0.90 bar. Determined from the N isotherm at P/P = 0.1 bar.
0
2
0
2
73 K and 6.9 wt % at 298 K (1 bar) for its dominant high BET
2
surface area, while the corresponding value for NPTN-1
containing carbazole moiety is slightly lower of 13.3 and 8.1 wt
%. These uptakes are comparable to many impressive examples
highest BET area of 1558 m /g with a total pore volume (V , P/P
t
0
3
=
0.9 bar) up to 1.23 cm /g, while the BET surface area and total
pore volume for NPTN-1 (1187 m /g, 0.93 cm /g) and NPTN-3
1055 m /g, 0.83 cm /g) are not much of a difference but slightly
lower relative to NPTN-2. Although the surface areas and pore
volumes were lower than those of most COFs and PAFs, these
values are still comparable with many other organic adsorbent-
2
3
12b
2
3
like PAF-18-OLi (14.4 wt %, 273 K, 1 bar), triptycene-based
(
microporous poly(benzimidazole) networks TBI-1 (14.0 wt %,
17b
35
273 K, 1 bar), and nanoporous porphyrin polymers Ni-Por-1
36a
(
13.8 wt %, 273 K, 1 bar), but lower than PAF-1-CH NH
2 2
35b
1
8a,36
(about 19.4 wt %, 273 K, 1 bar)
frameworks CTF-0 (15.7 wt %, 273 K, 1 bar). This high CO
and covalent triazine
s.
7c
2
Using nitrogen as probe, the experimental pore size
distributions for the NPTNs networks were obtained from the
adsorption isotherms by the nonlocal density functional theory
NLDFT). It is interesting to observe that all the samples have
almost same microporous and mesoporous sizes. Figure 3 shows
uptake capacity might be attributed to the presence of
heterocylics and strong polar surface interaction between the
network and guest gas molecule. Caused by low polarity of sulfur
atom and hence weak interaction, NPTN-3 shows the minimum
uptake capacities (9.8 wt %) in spite of its comparable specific
surface area and pore volume to NPTN-2. Because of the rich
nitrogen content, this capacity is still competitive with those of
many reported porous organic polymers with higher BET
surface, such as furan-based imine-linked POF-1 (7.7 wt %, 273
3
7
(
38
K, 1 bar), porous borazine-linked polymers BLP-1H (7.8 wt %,
3
9
2
2
73 K, 1 bar),1 and microporous cyanate resin CE-2 (7.9 wt %,
8a
73 K, 1 bar). With comparable surface area and pore volume,
it is usually envisioned that the N, O in NPTNs create a high
electric field on the network surface, leading to a high binding
force with quadrupolar CO molecules. Notably, NPTN-1 has a
2
higher CO uptake than NPTN-2 in the range of 0.01−0.6 bar as
2
evidenced by the sorption isotherms. This may indicate that
efficient doping of nitrogen helps to achieve a high CO uptake at
2
Figure 3. NLDFT pore size distribution curves of NPTNs.
low pressure regions, while doping of oxygen prefers to enhance
9
b,40
adsorption at relatively high pressure.
As a result, the CO2
capacities for the investigated NPTNs are not highly related to its
surface area but closely related to the surface nature.
that a large fraction of pores originating from microspores with a
diameter less than 20 Å range from 0.35 to 0.71 nm and 1.1 to 2.0
nm, while a considerable proportion of mesopores is broadly
distributed from 20 to 50 Å. The fraction of microporosity was
compared by the ratio of micropore volume to total pore volume
To gain further insights from the host−guest interaction, Q
2
st
(CO isosteric heat of adsorption) was obtained with the
Clausius−Clapeyron equation from the CO adsorption
2
41
isotherms at 273 and 298 K. All materials show a high Q for
st
(
V /V ), where V refers to the pore volume calculated from
CO (>30 kJ/mol) (Figure 5) at low coverage, and the Q is
0.1
t
0.1
2
st
N nitrogen sorption at 0.1 bar and V at 0.9 bar. Notably, NPTN-
2
lower than MOF materials of CuBTTri which possesses the
2
t
3
42
has the highest total pore volume of 1.23 cm /g, while its
highest Q for CO (96 kJ/mol) and MRF (>40 kJ/mol), but it
st
2
2
879
dx.doi.org/10.1021/ma500080s | Macromolecules 2014, 47, 2875−2882

Macromolecules
Article
Figure 6. IAST selectivity of NPTNs for CO (0.15 bar) over N (0.85
bar).
2
2
Figure 5. Isosteric heat of adsorption of CO versus the uptake amount.
2
isotherms for both CO and N are shown in Figures S19−24 at
2
2
is of the same level to many other POPs based on heterocyclic
43
273 K for pressures of 0−1 bar. NPTN-1−3 exhibit a
rings, such as HCP-1 (23.5 kJ/mol), CMP networks (27.0−
4
4
pronounced CO uptake and a fairly low N adsorption at
2
2
3
5
3.0 kJ/mol), and COFs (15−30 kJ/mol). As shown in Figure
pressure <1 bar. The different adsorption ability toward CO and
2
, the values are arranged in the following order: NPTN-2 (37
N provides a basis for the selective capture of CO from gas-
2
2
kJ/mol) > NPTN-1 (34 kJ/mol) > NPTN-3 (30 kJ/mol), which
mixture streams. CO /N selectivity depends on two aspects,
2
2
is consistent with that of the CO capacities. Comparatively
2
including the capacities of carbon dioxide and nitrogen. Both
strong interactions of guest molecules with the adsorbent walls,
improving CO and reducing N uptakes will be beneficial for the
2
2
which are heats of adsorption, are necessary for CO adsorption.
2
raise of selectivity. Typically, the CO uptake abilities at 273 K/1
2
Besides, other microporous parameters include pore shape,
degree of disorder, internal surface chemistry, or the free volume
bar were 3.01 mmol/g (13.3 wt %) for NPTN-1 and 3.18 mmol/
g (14.0 wt %) for NPTN-2, respectively. The corresponding
also play a role in CO sorption properties. A steeper downward
2
values for N uptake were 0.126 mmol/g (3.58 wt %) and 0.177
2
trend of the Q value for NPTN-1 leads to a weaker interaction
st
mmol/g (4.96 wt %) at the same condition, respectively. NPTN-
with CO than NPTN-2 with the increasing capacities. The CO2
2
1
displays a higher ideal selectivity (45) than NPTN-2 (22) for a
adsorption of NPTN-3 is lower than that of NPTN-1 and
NPTN-2, which mainly can be attributed to the tiny contribution
larger decrease of N uptake (1.38 wt %) than CO uptake (0.7
2
2
wt %). Here, a low uptake of N might be the controlling factor.
2
from heats of CO adsorption. Generally, isosteric heat of
2
NPTN-3 exhibits the lowest CO capacities but also the lowest
2
adsorption will be affected by the interaction between
N uptake (0.109 mmol/g), and hence the ideal selectivity is a
2
intersorbate and pore space, or the size distinctions between
45
litter higher than NPTN-2 of 25 (Table 2).
pore size distributions and adsorbed molecules and so on.
From these viewpoints, the difference of CO capacities and
2
Table 2. Summary of CO Uptakes for NPTNs
isosteric heat value can be explained. First, there are some
differences among the surface of three polymers. The
incorporation of triazine and heterocyclics with abundant
nitrogen and oxygen atom endow NPTN-1 and NPTN-2 high
surface polarity, which significantly enhance their affinity for
2
CO2273 K (wt %) CO2298 K (wt %) Q (kJ/mol) selectivity
st
a
polymer
NPTN-1
NPTN-2
NPTN-3
13.3
14.0
9.8
8.1
6.9
5.9
34
37
30
45
22
25
CO . Most possibly because of the largest physical polarity of
2
a
Calculated by the IAST model from 85% N and 15% CO at 273K
2
2
oxygen, NPTN-2 exhibits the highest Q value along with the
st
and 1 bar.
highest capacity for CO . Meanwhile, sulfur atom does a little
2
contribution to the interaction of the network with CO2,
The obtained ideal selectivity is comparable to many other
resulting the lowest Q value and CO uptake of NPTN-3.
st
2
46b,47
POPs,
This suggests that the introduction of carbazole has significantly
improved the selectivity of CTFs. The high CO /N selectivity of
and NPTN-1 overrates all other CTFs disclosed.
Second, the presence of ultramicropores always means a strong
affinity toward gas molecules, and hence such porous materials
show high gas uptakes at low pressures due to the overlap of the
potential fields from both sides of the pore walls.
2
2
NPTN-1 can be attributed to the stronger interaction with CO2
molecule than N . The presence of triazine groups and strong
To assess the potential in gas separation, some accounts can be
taken by considering CO /N selectivity. For evaluation of
2
polar surface accelerates the interactions with the polarizable
2
2
CO molecules through dipole−quadrupole interactions. Mean-
realistic postcombustion capture of CO , selectivity of CO over
2
2
2
while, NPTN-1 shows weaker affinity toward N comparing to
N at an equilibrium partial pressure of 0.85 bar (N ) and 0.15
2
2
2
NPTN-2 and other CTFs. Similar to −NN− reported,
bar (CO ) in the bulk phase was imitated by ideal adsorbed
2
11a
carbazole moieties display some N -phobic like nature.
solution theory (IAST) model according to many other studies
2
1
5b,46
However, possibly due to both strong affinity toward CO and
by the equation
2
N molecular, NPTN-2 shows the lowest ideal selectivity in spite
2
xi/xj
of its highest CO uptake. Although NPTN-2 has a marginally
2
Si/j
=
yi/yj
higher CO uptake than NPTN-1, it has a lower CO uptake and
2
2
a higher N adsorption in the low pressure region, which makes
2
where the idea selectivity refers to the first component over the
second, and x , x and y , y denote the molar fractions of species i, j
in the adsorbed and bulk phases, respectively. Adsorption
NPTN-1 a promising candidate for postcombustions.
At 77 K and 1 bar, NPTN-2 exhibits 1.44 wt % hydrogen
uptake (Figure S25). Similar to the CO isotherms, the H uptake
i
j
i
j
2
2
2
880
dx.doi.org/10.1021/ma500080s | Macromolecules 2014, 47, 2875−2882

Macromolecules
Article
has not reached saturation in the investigated pressure range,
implying that high storage can be expected at higher pressures.
The high adsorption capacity of NPTN-2 can refer to its polar
surface due to the presence of triazine ring and oxygen atom. The
adsorption enthalpy is always claimed to be the most effective
ACKNOWLEDGMENTS
■
We acknowledge the financially support from the National
Science Foundation of China (Nos. 21204103 and 21376272),
Hunan Provincial Natural Science Foundation of China
(
13JJ413), China Postdoctoral Science (2012M521535), State
48
parameter at low loadings for hydrogen storage at 77 K.
Typically, the Q value of NPTN-2 (Figure S26) decreases to
Key Laboratory of Advanced Technology for Materials Synthesis
and Processing (2012-KF-14), and State Key Laboratory of Fine
Chemicals (KF1206).
st
−1
within the range 4−9.6 kJ mol at higher hydrogen uptake,
which is typical for dispersive van der Waals interactions. It is
worthwhile to note that the Q value of NPTN-2 at low coverage
st
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