A fluorine-containing hydrophobic covalent triazine framework with excellent selective CO2 capture performance

Article abstract of DOI:10.1039/c7ta08913a

In this article, a set of fluorine functionalized covalent triazine-based frameworks have been designed and synthesized with 2,2′,3,3′,5,5′,6,6′-octafluoro-4,4′-biphenyldicarbonitrile as the monomer under typical ionothermal conditions. A prominent defluorination process during synthesis etches the networks to release CF_n, resulting in a significant loss of fluorine and carbon. Notably, the synergistic effects of polar C-F bonds and rich CO₂-philic N sites bestow upon the framework an excellent H₂ uptake (1.77 wt%, 77 K and 1 bar) as well as a significantly high CO₂ adsorption capacity (5.98 mmol g^-1, at 273 K and 1 bar), surpassing all related CTF materials measured under identical conditions that have been reported in the literature to date. Additionally, the material also exhibits a high CO₂/N₂ selectivity of 31 as predicted by the Henry model. The hydrophobicity of the CTF materials has been significantly enhanced owing to the incorporation of hydrophobic fluorine groups, which was further confirmed by ambient water vapor sorption.

Full text of DOI:10.1039/c7ta08913a

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2018, DOI: 10.1039/C7TA08913A.
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January 2016 Pages 1–330
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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
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ARTICLE
A fluorine-containing hydrophobic covalent triazine framework
with excellent selective CO capture performance
2
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
Guangbo Wang, Karen Leus, Himanshu Sekhar Jena, Chidharth Krishnaraj, Shuna Zhao, Hannes
a
a
b
a*
Depauw, Norini Tahir, Ying-Ya Liu and Pascal Van Der Voort
DOI: 10.1039/x0xx00000x
In this article, a set of fluorine functionalized covalent triazine-based frameworks have been designed and synthesized
with 2,2’,3,3’,5,5’,6,6’-octafluoro-4,4’-biphenyldicarbonitrile as the monomer under typical ionothermal conditions. The
www.rsc.org/
prominent defluorination process during synthesis etches the networks to release CF
fluorine and carbon. Notably, the synergistic effects of polar C-F bonds and rich CO
framework an excellent H uptake (1.77 wt%, 77 K and 1 bar) as well as a significantly high CO
mmol/g, at 273 K and 1 bar), surpassing all related CTF materials measured under identical conditions that have been
reported in the literature to date. Additionally, the material also exhibits a high CO /N selectivity of 31 predicted by the
n
, resulting in a significant loss of
-philic N sites bestow upon the
adsorption capacity (5.98
2
2
2
2
2
Henry model. The hydrophobicity of the CTF materials has been significantly enhanced owing to the incorporation of the
hydrophobic fluorine groups, which was further confirmed by ambient water vapor sorption.
materials are easily adjusted by careful selection of the structure-
directing monomers as building blocks. As far as functionalization of
the monomer is concerned, replacing hydrogen by nitrogen or
fluorine atoms has proven to be beneficial for gas
Introduction
Until today, the development of effective technologies or strategies sorption/purification and heterogeneous catalysis due to the strong
for capturing or eliminating CO produced from various processes, electrostatic interactions of specific gas molecules or catalytically
2
in order to minimize its influence on climate change remains an active metal sites with the heteroatoms in the pore walls of porous
1
-4
24-26
urgent and challenging task. Recently, a new class of designable materials.
Within this context, Lotsch et al. reported a series of
and robust porous organic polymers (POPs), including metal organic nitrogen-rich CTFs as high-performance platforms for selective CO
2
5
-7
8, 9
frameworks (MOFs) and covalent organic frameworks (COFs)
,
capture and storage. Notably, the CO
2
uptake of bipyridine-CTF
have demonstrated significant promise for gas sorption and synthesized at 600 °C reached up to 5.58 mmol/g at 273 K and 1
1
5
separation. To address and tackle the CO2 challenges, we have bar. Very recently, Palkovits et al. reported a class of N-doped CTF
focused on a nitrogen-rich subclass of POPs, namely covalent materials, that exhibit the highest adsorption capacities of H (2.63
triazine frameworks (CTFs), which exhibits promising potential in a wt% at 1 bar and 77 K) and CO (5.97 mmol/g at 273 K and 1 bar) to
Besides the introduction of nitrogen groups, the
incorporation of fluorine functional groups into porous materials
2
2
1
0-15
12
variety of applications including gas adsorption and separation,
date.
1
2, 16-18
19, 20
heterogeneous catalysis
and waste water treatment
owing to their remarkably large surface area, low skeleton density, (e.g. MOFs, COFs) has been extensively studied because of its
good thermal and chemical stability combined with enhanced hydrophobicity as well as its potential influence on gas sorption
2
7-29
tunability and functionality. Since the pioneering work of Kuhn et al. properties and catalytic activities.
in 2008, who developed the first covalent triazine framework, fluorinated CTF materials remain few.
denoted as CTF-1, by trimerization of 1,4-dicyanobenzene in synthesized a perfluorinated covalent triazine-based framework,
However, reports on
1
4, 30
Firstly, Han et al.
1
0
presence of ZnCl
considerable efforts have been devoted to design and synthesis of monomer, exhibiting extremely high CO
2
under typical ionothermal conditions,
named as FCTF-1-600, with tetrafluoroterephthalonitrile as the
uptake (1.76 mmol/g at
273 K and 0.1 bar and 5.53 mmol/g at 1 bar) and an exceptional
2
2
1-23
various CTFs materials and explore their potential applications.
In principle, the structure and functionalities of this type of CO
perfluorinated CTFs, fluorinated microporous organic polymers (F-
MOPs) showed a twofold increase in the CO adsorption capacity in
comparison to the corresponding non-functionalized MOPs.
1
4
2
2
/N selectivity of 77 under kinetic flow conditions. Apart from
2
31
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In this work, we report on a set of fluorine-containing covalent materials with higher nitrogen content, surface area and porosity in
triazine framework, identified as F-DCBP-CTFs, by trimerization of comparison to the materials obtained using a ZnCl /monomer ratio
,2’,3,3’,5,5’,6,6’-octafluoro-4,4’-biphenyldicarbonitrile (F-DCBP) via of 10. More interestingly, the obtained F-DCBP-CTF materials have a
ionothermal synthesis conditions at 400 ºC using different much higher nitrogen content in comparison to the non-
ZnCl /monomer ratios (Figure 1) (See the detailed synthesis and functionalized DCBP-CTF compounds, which are supposed to be one
characterizaꢀon in Electronic Supporꢀng Informaꢀon, ESI†, Figure of the beneficial binding sites for enhanced CO adsorption uptake
2
2
2
2
S1-S3). The obtained F-DCBP-CTF materials were comprehensively in this framework. In all cases, the total amount of elements
characterized. Remarkably, they exhibit relatively large surface determined by EA is always lower than 100%, the residue mass can
areas and pore volumes, significantly high CO
capacities as well as high CO /N selectivity, outperforming most of could not be removed completely.
the reported POPs to date. Furthermore, water vapor adsorption information about the structure of the materials, solid state cross-
2 2
and H adsorption be assigned to trapped metal salts and water in the pores, which
1
0, 15
2
2
To obtain more detailed
1
3
19
measurements confirmed significant enhancement of the polarization magic angle spinning (CP/MAS) C and F NMR
hydrophobicity of the materials in comparison to the non- experiments were performed on all the CTF materials. As shown in
functionalized analogues
.
Figure S6, ESI†, the broad peak at 126 ppm corresponds to the
aromatic carbons. It is however difficult to distinguish the positions
of the various aromatic carbons owing to the partial graphitization,
2
2, 32
previously reported.
The presence of fluorine groups in the
1
9
structure was confirmed by F NMR measurements, since the
signal for carbon-fluorine at approximately 137 ppm was clearly
3
3
detected (Figure S7, ESI†). Additionally, X-ray photoelectron
spectroscopy (XPS) measurements were performed to get more
insights into the chemical states of the elements in the CTFs
materials (Figure 2 and Figure S8-S10). For F-DCBP-CTF-1, the C 1s
spectrum can be deconvoluted into three peaks. The dominant
2
peak at 284.8 eV is related to the aromatic sp carbon and the peak
at 286.1 can be assigned to the triazine or nitrile carbon. The less
1
4,
pronounced peak at 288.1 eV is associated with carboxyl groups.
3
0
The N1s spectrum is divided into three peaks as well. The first
34
Figure 1. Reaction scheme and schematic structure of F-DCBP-CTFs. (* 10% of
theoretical fluorine atoms are retained in the framework)
peak at 399 eV is related to the nitrile species, the peak at 400.5
30
eV is attributed to pyrrolic/pyridonic-N species and the peak at
34
4
03.2 eV is assigned to the oxidized N-O species . The single peak
at 687.6 eV in the F 1s spectra of the F-DCBP CTFs corresponds to
2
0
the aromatic C-F bond . The fluorine content was determined by
XPS measurements. We note that the synthesized F-DCBP-CTFs only
contain about 10 % of the theoretical fluorine atoms. Specifically,
the fluorine content amounts 4.20 % for F-DCBP-CTF-1 and 3.13 %
for F-DCBP-CTF-2, which is much lower than the theoretical value
Results and discussion
Synthesis and characterization of the CTF materials
The porous materials were prepared at 400 °C under typical
ionothermal conditions using molten ZnCl
The obtained F-DCBP-CTFs were identified as F-DCBP-CTF-1 and F-
DCBP-CTF-2 when a ZnCl /monomer ratio of 5 and 10 was applied,
respectively. For comparison, non-functionalized CTFs based on
,4’-biphenyldicarbonitrile (DCBP) as the monomer were also
2
as Lewis acid catalyst.
(
43%). The much lower F content is mainly because of the
elimination of fluorine and the slight difference between F-DCBP-
CTF-1 and F-DCBP-CTF-2 is due to the fact that ZnCl2 is able to
2
4
prepared and will be referred to as DCBP-CTF-1 and DCBP-CTF-2 in
the following. It should be noted that at a high temperature, the
fluorine groups partially decomposed, confirmed by the gas release
while opening the glass ampoules. Such gas release was also
observed in the earlier reported FCTF-1 and the as-formed gases
1
4
were identified as CF
synthesized materials was examined by powder X-ray diffraction
Figure S4, ESI†). As expected, all the CTFs are amorphous. The
successful trimerization reaction was indicated by FT-IR
4
, C
2
F
4
and F
2
.
The crystallinity of the
(
-1
measurements (Figure S5, ESI†). The weak band at 2230 cm for F-
DCBP-CTFs points to the incomplete polymerization of the nitrile
-1
groups, while the characteristic weak bands at 1560 and 1380 cm
1
5, 22
can be assigned to the triazine rings.
revealed that the nitrogen and carbon contents for the synthesized
Elemental Analysis (EA)
1
0
DCBP-CTF materials are in accordance with the literature. As
outlined in Table 1, a ZnCl /monomer ratio of 5 resulted in the CTF
Figure 2. C 1s, N 1s and F 1s spectra of F-DCBP-CTF-1
2
2
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induce and accelerate the defluorination process, thereby isotherms at high relative pressure (P/P
generating different materials under different ZnCl
0
> 0.9), indicating meso-
2
/monomer /macropores presence to be attributed to interparticulate voids
Table 1. Elemental analysis and pore characteristics of all the synthesized CTF materials.
0 0 0
a). BET surface area calculated over the pressure range 0.01-0.05 P/P at 77 K; b). V0.1, pore volume at P/P = 0.1 at 77 K; c). Vtot, total pore volume calculated at P/P =
0
.98; d) determined by XPS.
3
0
36
ratios. .
that exist between the highly aggregated particles. As summarized
High angle annular dark field scanning-transmission electron in Table 1, the Brunauer-Emmett-Teller (BET) surface area and pore
2
microscopy (HAADF-STEM) and corresponding energy dispersive X- volume for DCBP-CTF-1 is calculated to be 2437 m /g and 1.48
3
ray spectroscopy (EDX) mapping images of F-DCBP-CTF-1 (Figure 3) cm /g, respectively. In contrast, the F-DCBP-CTF-1 exhibits a slightly
2
3
and F-DCBP-CTF-2 (Figure S11, ESI†) show that C, N and F elements lower surface area and pore volume of 1574 m /g and 1.5 cm /g,
are well dispersed and homogeneously distributed throughout the respectively.
materials. Scanning electron microscopy (SEM) images show that all
the CTF materials are composed of tiny particles with irregular
shapes and sizes (Figure S12 and Figure S13, ESI†). The thermal
stability of all the studied CTF materials was determined by
thermogravimetric analysis (TGA) of which results indicate that the
F-DCBP-CTF materials are stable up to 400 °C, thus slightly lower
than the DCBP-CTF materials (Figure S14, ESI†). This can be
attributed to the strong electron withdrawing effect of the fluorine
35
atoms in the framework.
The porous nature and high nitrogen content along with the
introduction of fluorine groups into the F-DCBP-CTF materials make
them promising candidates for gas sorption and separation.
2
Accordingly, the CO adsorption isotherms for both DCBP-CTFs and
F-DCBP-CTFs up to 1 bar at 273 K and 298 K were recorded (Figure 5
and Figure S15-S16, ESI†). In general, the materials synthesized with
Figure 3. High angle annular dark field scanning-transmission electron
microscopy (HAADF-STEM) and corresponding energy dispersive X-ray
spectroscopy (EDX) mapping images of carbon (red), nitrogen (green)
and fluorine (blue) on the sample of F-DCBP-CTF-1.
the ZnCl /monomer ratio of 5 show a better performance in CO2
2
adsorption compared to those prepared with a ZnCl /monomer
2
ratio of 10, due to the higher microporosity, nitrogen content and
fluorine groups of the materials (Table 1). Noteworthy, F-DCBP-CTF-
Gas sorption properties
1
3
exhibits a significantly high CO adsorption capacity of 5.98 and
The porosity of all the obtained CTF materials was determined by
nitrogen adsorption measurements collected at 77 K (Figure 4). At
2
.82 mmol/g at 273 K and 298 K and 1 bar, respectively (Table 2,
entry 1). To the best of our knowledge, this value represents the
highest CO2 adsorption capacity for all the CTF materials
synthesized at 400 ºC reported thus far, as summarized in Table 2
and Table S1, ESI†. It should be noted that direct comparison of the
relative low pressure, all the isotherms exhibit a high N
indicating typical microporous character. Notably, for DCBP-CTF-2, a
type IV isotherm with a H hysteresis loop in the desorption branch
2
uptake,
2
is obtained, typical for mesoporous materials according to the
IUPAC classification. In contrast to DCBP-CTF-2, the F-DCBP-CTF
materials give rise to the type I isotherms with a steep rise of the
materials’ CO adsorption capacities remains difficult as they are
2
synthesized under different conditions and will partially or
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Table 2. Summary and comparison of the gas sorption properties of the studied materials and the reported CTF materials.
CO
2
uptake
H
2
uptake
(wt%)
2
N uptake
max
Ref.
Q
st
2 2
CO /N
(mmol/g)
(mmol/g)
Sample
(
kJ/mol)
Selectivity
2
73 K
298 K
3.82
77 K
1.77
298K
0.28
F-DCBP-CTF-1
5.98
33.1
31
F-DCBP-CTF-2
DCBP-CTF-1
DCBP-CTF-2
FCTF-1
5.23
3.65
3.31
4.67
4.55
3.16
2.07
1.84
3.21
2.72
-
0.29
0.24
0.13
-
-
24.1
-
22
13
21
This work
-
-
-
a
-
31
14
15
lut-CTF400
1.36
0.20
37.5
63
a
F-CTF-1-600
5.53
5.58
3.41
2.95
-
-
-
19
14
15
Bipy-CTF-600
HT
CTF-py
2.1
0.28
34.4
37
5.97
6.3
4.22
4.8
2.63
-
0.25
0.44
27.1
27.1
29
12
11
HAT-CTFs
126
2 2
a). CO /N selectivity was calculated by Ideal Adsorption Solution Theory (IAST).
completely carbonize at high temperatures, hence they are not We calculated the selectivity of all the CTF materials using the ratio
CTFs anymore and normally called triazine-based porous carbon of the initial slopes in the Henry region of the CO and N
materials. More importantly, the realistic flue gas generally contains adsorpꢀon isotherms at 298 K. (Figure S18 and S19, ESI†). The
approximately 15 % CO at a total pressure of 1 bar, thus, the calculated values are listed in Table S1 and a remarkable CO /N
adsorption of CO at ~0.15 bar is more relevant to the realistic CO selectivity of 31 was achieved by F-DCBP-CTF-1, much higher than
capture. Remarkably, at 0.15 bar and 273 K, F-DCBP-1 can adsorb that of DCBP-CTF-1 (13). The higher CO /N selectivity further
.15 mmol/g CO , while at 298 K, this capacity only decreases emphasizes the synergistic effects of microporosity and rich CO
moderately to 1.19 mmol/g, remaining significantly higher than philic sites (N and F) within these polymeric networks. As such,
2
2
2
2
2
2
2
2
2
2
2
2
-
3
7
most of the reported porous organic polymers. The remarkable given the exceptionally high CO
enhanced CO adsorption capacity for F-DCBP-CTF-1 can be intrinsic high thermal and chemical stability, these materials seem
attributed to the strong electrostatic interactions between CO to be plausible adsorbents for practical application in
2
adsorption capacity and the
2
2
a
molecules and the polar C–F bonds in the skeleton. Additionally, postcombustion CO
incorporation of nitrogen in POPs materials has already been
2
capture.
1
5, 38
proven to enhance the adsorption capacity of CO
observation in line with our findings that F-DCBP-CTFs have a much
higher nitrogen content and for this reason a higher CO adsorption
capacity compared to the DCBP-CTF materials. The outstanding CO
2
,
an
2
2
uptake at both low and moderate pressure together with the
remarkable water tolerance and high thermal and chemical stability
of the perfluorinated CTFs make them promising adsorbents for CO
capture from flue gas. To provide a better understanding of the CO
2
2
adsorption in the studied CTFs, we have also calculated the isosteric
heat of CO adsorption (Qst) for both DCBP-CTF-1 and F-DCBP-CTF-1
materials using the Clausius-Clapeyron equation to fit CO
adsorption isotherms at 273 K and 298 K and plotted it as a function
of the capacity of adsorbed CO (Figure S17, ESI†). The Qst value at
low CO adsorption uptake was calculated to be ~33.1 kJ/mol for F-
DCBP-CTF-1, indicating the strong dipole-quadrupole interactions
between CO molecules and the framework of F-DCBP-CTF.
Additionally, the lower st value also means much lower
regeneration cost of this material compared to conventional amine
2
2
2
2
2
Q
3
9
solutions. The incorporation of fluorine groups into CTF materials
As a potential renewable and clean alternative to current fossil-fuel,
hydrogen storage remains a major obstacle for its widespread
implementation. Recently, adsorptive hydrogen storage in porous
not only resulted in enhanced CO adsorption capacities but also
2
afforded more preferential adsorption of CO over N , i.e., higher
2
2
CO /N selectivity, another crucial factor for realistic CO capture.
2
2
2
4
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materials (e.g. MOFs, COFs) has been explored as a possible capacity of 253 cm /g (0.21 g/g) at P/P
ARTICLE
3
0
= 0.9 and 293 K. This clearly
4
0-42
approach for hydrogen storage.
performed H adsorption measurements at 77 K up to 1 bar with DCBP-CTF has been significantly enhanced after perfluorine
those materials that showed higher CO uptake capacities (Figure 6 functionalization, mainly due to the hydrophobicity of the fluorine
and Table S1, ESI†). As shown in Figure 6, the H adsorption capacity groups present in the framework that hinders the entrance of water
of DCBP-CTF-1 reaches 1.6 wt%, comparable to the previously molecules into the cavities easily.
For this reason, we further demonstrates that the hydrophobicity of the pore surface of F-
2
2
2
1
0
reported result. Notably, F-DCBP-CTF-1 exhibits a higher H
2
uptake
1
2
of 1.77 wt%, surpassing most of the reported CTF materials and
4
3
Conclusions
ranking only slight below fl-CTF-400 (1.95 wt%) and PCTF-1 (1.86
4
4
wt%) measured under identical conditions.
In summary, a class of robust and hydrophobic fluorine-containing
covalent triazine-based frameworks with large surface areas was
synthesized under ionothermal conditions. Trimerization of the
perfluorinated monomer and subsequent defluorination
carbonization process of the network results in a significant loss of
fluorine and carbon, yielding nitrogen-rich materials. The obtained
porous materials display exceptionally high CO
capacities. The H uptake for F-DCBP-CTF-1 can reach 1.77 wt% at
7 K and 1 bar, while the maximum CO adsorption capacity for F-
2 2
and H uptake
2
7
2
DCBP-CTF-1 is up to 5.98 mmol/g at 273 K and 1 bar (2.15 mmol/g
at 273 K and 0.15 bar), exceeding most of the reported POPs
materials in the literature to date. The perfluorinated CTFs also
2 2
exhibit relatively high CO /N selectivity compared to the non-
functionalized CTFs. Moreover, in comparison to the DCBP-CTF
materials, the hydrophobicity of the F-DCBP-CTF materials has been
significantly enhanced due to the hydrophobic nature of the C–F
bonds, confirmed by ambient water vapor sorption measurements.
This highly fluorinated hydrophobic porous materials are not only of
great interest for gas sorption and separation, but they also can be
Water vapor sorption
To date, there are only few studies on the water sorption used for a wide range of applications including water/oil separation,
1
3, 15
characteristics of CTFs.
The hydrophobicity of the fluorine capture of bio-renewable resources from water.
groups prompted us to explore the potential of the CTFs materials
for water vapor sorption (Figure 7 and Figure S20, ESI†). As shown
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
G. W. thanks the China Scholarship Council (CSC) and UGENT
BOF grant for PhD Funding. K. L. acknowledges the financial
support from Ghent University. H. S. J. thanks FWO
[
6
PEGASUS]2 Marie Sklodowska-Curie grant agreement No
65501 for incoming post-doctoral fellowship. S.-N. Z.
acknowledges the postdoctoral scholarship of the Ghent
University Special Research Fund (BOF.PDO.2016.0030.01). H.
D. thanks the Research Foundation Flanders (FWO-
Vlaanderen) Grant (No. G.0048.13N.). Y.-Y. L. thanks the
financial support of China Ministry of Science and Technology
(
2016YFE01069800) and National Natural Science Foundation
of China (21403025). The authors would like to thank Katrien
Haustraete for STEM and EDX mapping measurements. Dr.
in Figure 7, both CTF materials exhibit a type V isotherm, in which Johannes Schmidt is acknowledged for XPS measurements.
water molecules are only slightly adsorbed at low relative pressure,
revealing the hydrophobic character of the pores, followed by a
Notes and references
steep increase of water uptake at high relative pressures. A total
3
water adsorption capacity of 630 cm /g (0.51 g/g) for DCBP-CTF-1 is
obtained whereas the F-DCBP-CTF-1 only exhibits an adsorption
1
.
Z. J. Zhang, Z. Z. Yao, S. C. Xiang and B. L. Chen, Journal,
2014, 7, 2868-2899.
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