Covalent Triazine Frameworks via a Low-Temperature Polycondensation Approach

Article abstract of DOI:10.1002/anie.201708548

Covalent triazine frameworks (CTFs) are normally synthesized by ionothermal methods. The harsh synthetic conditions and associated limited structural diversity do not benefit for further development and practical large-scale synthesis of CTFs. Herein we report a new strategy to construct CTFs (CTF-HUSTs) via a polycondensation approach, which allows the synthesis of CTFs under mild conditions from a wide array of building blocks. Interestingly, these CTFs display a layered structure. The CTFs synthesized were also readily scaled up to gram quantities. The CTFs are potential candidates for separations, photocatalysis and for energy storage applications. In particular, CTF-HUSTs are found to be promising photocatalysts for sacrificial photocatalytic hydrogen evolution with a maximum rate of 2647 μmol h^?1 g^?1 under visible light. We also applied a pyrolyzed form of CTF-HUST-4 as an anode material in a sodium-ion battery achieving an excellent discharge capacity of 467 mAh g^?1.

Full text of DOI:10.1002/anie.201708548

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Accepted Article
Title: Covalent Triazine Frameworks via a Low Temperature
Polycondensation Approach
Authors: kewei Wang, Liming Yang, Xi wang, Liping Guo, Guang
Cheng, Chun Zhang, Shangbin Jin, Bien Tan, and Andrew
Cooper
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201708548
Angew. Chem. 10.1002/ange.201708548
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Angewandte Chemie International Edition
10.1002/anie.201708548
COMMUNICATION
Covalent Triazine Frameworks via a Low Temperature
Polycondensation Approach
[a]
[a]
[b]
[a]
[a]
[c]
Kewei Wang, Li-Ming Yang, Xi Wang, Liping Guo, Guang Cheng, Chun Zhang, Shangbin
[a]
[a]
[a,d]
Jin,* Bien Tan,* and Andrew Cooper
Abstract: Covalent triazine frameworks (CTFs) are normally
synthesized by ionothermal methods. The harsh synthetic conditions
and associated limited structural diversity do not benefit for further
development and practical large-scale synthesis of CTFs. Herein we
report a new strategy to construct CTFs (CTF-HUSTs) via a
polycondensation approach, which allows the synthesis of CTFs
reaction medium.[5a] This method can lead to CTFs with a degree
of crystalline order, but the high reaction temperatures cause the
partial carbonization of the structure and the materials are
obtained in the form of black powders. Hence, CTFs prepared by
this method lack an electronic band gap and may be unsuitable
for photophysical applications. Furthermore, these reaction
temperatures consume a large amount of energy and preclude all
but the most stable building blocks, thus limiting the scope for
scale up and synthetic diversity. It is, therefore, imperative to find
new methods for the synthesis of CTFs under milder conditions.
Previous research has shown that CTFs could be synthesized at
room temperature, and catalyzed by strong and corrosive acid
such as trifluoromethylsufonic acid.[7a,7b] This avoids
carbonization, but the method is obviously not suitable to acid-
sensitive building blocks, and also the resulting materials did not
have layered structures.
under mild conditions from
a wide array of building blocks.
Interestingly, these CTFs display a layered structure. The CTFs
synthesized were also readily scaled up to gram quantities. The CTFs
are potential candidates for separations, photocatalysis and for
energy storage applications. In particular, CTF-HUSTs are found to
be promising photocatalysts for sacrificial photocatalytic hydrogen
-1
-1
evolution with a maximum rate of 2647 µmol h
g under visible light.
We also applied a pyrolyzed form of CTF-HUST-4 as an anode
material in a sodium-ion battery achieving an excellent discharge
-1
capacity of 467 mAh g .
Here, we develop a new strategy involving the condensation
reaction of aldehydes and amidines to construct CTFs under mild
conditions (Scheme 1). The newly-synthesized CTFs possess
layered structures, high surface areas, and tunable functions and
geometries. An important feature of this method lies in the
relatively gentle reaction conditions (≤120 °C, no strong acids).
This general method enables CTFs to be easily scaled up to
multigram level with no special apparatus. The materials are
Covalent organic frameworks (COFs) are an emerging class of
porous materials, characterized by their ordered structures, high
surface areas, and structural diversity.[ They have shown
promise in applications such as gas adsorption,[2] catalysis,[3] and
1]
optoelectronics.[4] A variety of methods have been reported to
prepare COFs, such as polycondensation,[
1a,4a]
cyclization
reactions,[ or surface mediated methods.
5]
[1b,6]
Covalent triazine
frameworks (CTFs) are related to COFs and are typically
constructed through cyclization reaction of nitrile aromatic
building blocks; they feature high physicochemical stability and
high nitrogen content.[
5, 7]
Because of these characteristics, CTFs
have found diverse applications in gas adsorption and
storage,[5a,7a,7b] catalysis,[7c,7d,7e] and energy storage.[7f,7g] There
are still, however, a limited number of approaches for the
synthesis of CTFs.[
5a,7a]
The most common approach is
ionothermal synthesis at high temperatures (≥400 °C), which also
requires a large amount of ZnCl to serve as both catalyst and
2
[a]
K. Wang, Prof. L. Yang, L. Guo, G. Cheng, Prof. S. Jin, Prof. B. Tan
Key Laboratory of Material Chemistry for Energy Conversion and
1
Storage, Ministry of Education, School of Chemistry and Chemical
Engineering, Huazhong University of Science and Technology，
Luoyu Road No. 1037, 430074, Wuhan, China.
E-mail: jinsb@hust.edu.cn, bien.tan@mail.hust.edu.cn
Prof. X. Wang
School of Science, Beijing Jiaotong University, No.3 Shangyuancun,
Haidian District, 100044, Beijing, China.
Prof. C. Zhang
[
b]
c]
[
College of Life Science & Technology, Huazhong University of
Science and Technology, Luoyu Road No. 1037, 430074, Wuhan,
China.
Prof. A. Cooper
Department of Chemistry and Materials Innovation Factory,
University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.
Scheme 1. A scheme showing reaction mechanism for CTF-HUST synthesis.
(
a) Reaction mechanism for triazine formation in the synthesis of CTF-HUST;
representative structures of (b) CTF-HUST-1, (c) CTF-HUST-2, (d) CTF-HUST-
, and (e) CTF-HUST-4; the circles filled with different colors represent the
[d]
3
presence of two types of pores. “HUST” is the abbreviation of “Huazhong
University of Science and Technology”.
Supporting information for this article is given via a link at the end of
the document.
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COMMUNICATION
The successful formation of the triazine fameworks was
confirmed by Fourier-transformed infrared (FT-IR) analysis, in
which the characteristic vibrations from the triazine units at 1523
and 1367 cm−1 were observed for all CTF-HUSTs (Figure S2), in
good agreement with those of a small-molecule model compound
(
Figure S2). The solid-state cross-polarization magic angle
spinning carbon-13 nuclear magnetic resonance (CP-MAS 13C-
NMR) also unambiguously confirmed the formation of triazine
structures in CTF-HUSTs, where the chemical shifts at 122.0 and
132.4 ppm can be assigned to phenyl carbons and the chemical
shift at 165.4 ppm is assigned to the carbon signal from triazine
rings (Figure S3). Particle-like morphologies were observed by
field-emission scanning electron microscopy (FE-SEM) (Figure
S4). The CTF-HUSTs also show high thermal stability and are
stable up to 550 ºC without significant loss of mass, as revealed
by thermal gravimetric analysis (TGA) measurements (Figure S5).
Elemental analysis shows that the carbon and nitrogen contents
are close to theoretical results (Table S2).
Figure 1. (a) PXRD pattern of experimental (blue), simulated AA stacking
To investigate whether these framework materials have any
long range ordering, we used powder X-ray diffraction (PXRD).
Despite the extensive optimization efforts, no crystalline CTFs
were obtained. While these CTFs do not exhibit long-range
crystalline order (Figure 1a and Figure S6-S7), PXRD data for
CTF-HUST-1 showed two broad peaks at 7.6° and 25.8° (Figure
(black) and simulated AB stacking (red) of CTF-HUST-1, (b) High-Resolution
TEM image of CTF-HUST-1; (c) Atomic force microscopy topography of CTF-
HUST-1; (d) Height profile of AFM of the corresponding edge height of CTF-
HUST-1.
generally yellow or orange powders, which retain their optical
band gap, suggesting potential applications in photophysical
applications.[8] Intriguingly, the CTFs display a layered structure
and opening up a route to new type of nitrogen-doped layered
materials. These CTFs could be promising materials for the
applications in photocatalaysis and energy storage, as
exemplified here for photocatalytic sacrificial hydrogen evolution
and in the formation of a sodium-ion battery anode.
1a, blue curve). CTF-HUST-2 exhibited two features at
approximately 6° and 25° (Figure S7a, blue curve); CTF-HUST-3
contained two features at approximately 8° and 22° (Figure S7d,
blue curve), and CTF-HUST-4 showed two features at around 6°
and 21° (Figure S7g, blue curve). These features are very broad,
even with respect to the relatively broad peaks observed for CTFs
produced by ionothermal routes,[ and it is not possible to match
these to a specific structural model. These features do suggest,
however, the possibility of at least partially layered structures.
We further characterized the materials by high-resolution
transmission electron microscopy (HR-TEM) and atomic force
microscopy (AFM) as shown in Figure 1 and Figure S8a-c. HR-
TEM images are consistent with extended porous network
structures. By carefully observing the HR-TEM images, we
noticed that the CTFs seem to show stacking or layer structures
on their particle edges (Figure 1b and Figure S8a-c). We further
confirmed the layer structures in these CTFs by AFM imaging. We
found that these CTFs can indeed exist as sheets that seem to be
just a layers thick, when prepared by solvent-assisted sonication
in solvents such as ethanol. These CTF-HUSTs could be well
7b]
The CTF materials were synthesized via a condensation
reaction between an aldehyde and an amidine dihydrochloride
involving a Schiff base formation followed by a Michael addition.[
This is the first time that this type of condensation reaction has
been used for the synthesis of porous organic materials. The
CTFs prepared from four aldehydes, 1,4-benzene-dialdehye, 4,4'-
biphenyl-dialdehyde, tris(4-formylphenyl)-amine, and tris(4-
formylbiphenyl)-amine, were named as CTF-HUST-1, CTF-
HUST-2, CTF-HUST-3 and CTF-HUST-4, respectively (Scheme
9]
1). CTF-HUST-1 was used as a model to optimize the reaction
conditions. After screening different solvents, the optimal solvent
was found to be dimethyl sulfoxide (DMSO) (Table S1). The
optimal reaction conditions involved the use of cesium carbonate
(
2 3
Cs CO ) as a base, DMSO as a solvent, and a reaction
dispersed into ethanol, with concentration to be about 0.1 mg mL-
temperature of 120 °C. As a comparison, solvothermal methods
involving a closed reactor, as often used in the COFs syntheses,
were also used for the CTF-HUST-1 preparation but no significant
improvement in yield or properties was observed. Scalability is a
key requirement for practical applications of new materials. We
believe that this process could easily be scaled up because it is a
one-pot polymerization carried out at relatively low temperature
and ambient pressure, without protection by an inert atmosphere,
using a cheap catalyst and a relatively acceptable solvent. We
successfully scaled up the polymerization of CTF-HUST-1 to 5
grams scale, without the use of any special equipment (Figure S1),
and we believe that much larger scale syntheses should also be
possible.
1
(
Figure S9) and AFM characterization was performed by first
dispersing the samples in ethanol (Figure 3b and Figure S8d-f).
For instance, CTF-HUST-1 in ethanol was observed to have
lamellar layers with thickness of 1.06 nm, whereas CTF-HUST-2,
CTF-HUST-3 and CTF-HUST-4 give lamellar layers with
thickness of 1.15 nm, 1.01 nm and 0.80 nm, respectively (Figure
1b and Figure S8g-i). Some multilayered structures could also be
observed by AFM (Figure S10). For instance, multilayered CTF-
HUST-1 that are observed to bear an average layer thickness to
be around 3.26 nm. Therefore, these results showed that the
present CTF-HSUTs are layered materials, or at least that a
dispersible proportion of the sample is thus structured.
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(
Figure S11b), which is in a good range for CO
applications and higher than reported for CTF-1 (27.5 kJ mol ).
Indeed, the CO adsorption heat for these CTF-HUSTs is higher
2
capture
−
1 [11]
2
than for most other nitrogen-rich porous organic frameworks,
including porous benzimidazole polymers,[12] electron-rich
organonitridic
frameworks,[13]
conjugated
microporous
polymers,[ and hypercross-linked polymers.
14]
[15]
We also studied the optical properties of these CTF-HUST
samples and found that these materials could absorb light in the
visible region up to around 650 nm (Figure 3a-e). The band gaps
were calculated for these CTF-HUSTs on the basis of their UV-
visible absorption spectra. It was found that CTF-HUST-4 has the
smallest band gap of 2.13 eV and CTF-HUST-2 has the largest
gap (2.42 eV). The band gaps of CTF-HUST-1 and CTF-HUST-3
are 2.33 eV and 2.22 eV, respectively. The optical photographs
of solid state CTF-HUSTs are shown in Figure 3b-3e, showing
that the colors of the samples are in line with their absorption
properties. The different optical band gaps in this series indicate
Figure 2. (a) Nitrogen sorption curves and (b) corresponding pore size
distributions of CTF-HUST-1(black curve), CTF-HUST-2 (red curve), CTF-
[8c]
that the band gaps are tunable by varying the building blocks.
The CTFs synthesized by conventional methods have been
explored in photocatalysis, such as photocatalytic water splitting,
HUST-3 (blue curve) and CTF-HUST-4 (wine curve); (c) H
CTF-HUST-1 (black curve), CTF-HUST-2 (red curve), CTF-HUST-3 (blue
curve) and CTF-HUST-4 (magenta curve); (d) CO sorption curves of CTF-
2
sorption curves of
2
because of their analogous structures to graphitic carbon
HUST-1(black curve), CTF-HUST-2 (red curve), CTF-HUST-3 (blue curve) and
CTF-HUST-4 (magenta curve) at 273 K.
[16]
nitrides.
However, the photocatalytic activities are far from
satisfactory. Combining layer structures with above-mentioned
optical properties of CTF-HUSTs (tunable band gaps and broad
visible absorption, Figure 3a), CTF-HUSTs are particular
interesting for photocatalysis applications. We thereby tested our
newly synthesized CTF-HUSTs in sacrificial photocatalytic water
splitting under visible light (>420 nm, Figure 3f). CTF-HUST-1
showed a hydrogen evolution rate as 1460 µmol h-1 g-1, which is
higher than reported for CTF-1 synthesized by a modified
We next investigated the porosity of the CTF-HUSTs. First, the
materials were examined by nitrogen sorption experiments at
77 K. The surface areas and pore dimensions were evaluated
based on Brunauer–Emmett–Teller (BET) and Langmuir methods,
respectively. As shown in Figure 2a, the nitrogen adsorption
isotherms of the CTF-HUSTs exhibit a steep rise at low relative
pressure (P/P
0
< 0.001), indicating a microporous structure. For
~ 1)
ionothermal method (1072 µmol h-1 g ).
-1
[16a]
CTF-HUST-2 showed
the highest photocatalytic hydrogen evolution rate in this series of
CTF-HUST-2, the additional steep rise at high pressure (P/P
0
may be due to condensation in macropores formed between the
highly aggregated particles.[10] Nitrogen adsorption and
2647 µmol h-1
g . CTF-HUST-3 and CTF-HUST-4 exhibited
-1
-1
-1
-1
hydrogen evolution rates of 1238 µmol h
g and 1582 µmol h
desorption isotherms for CTF-HUST-4 show a clear hysteresis
loop, which indicates the presence of mesopores. The calculated
surface areas and pore volumes are summarized in Table S4. The
pore size distributions of CTF-HUSTs were calculated by using a
nonlocal density functional theory (DFT) method (Figure 2b). A
pore size of around 12 Å was observed for all the CTFs, in
agreement with theoretical values calculated from the idealized,
crystalline models for the four CTF-HUSTs (Scheme 1, green
circles). The second type of pore apertures suggested by
simulations for CTF-HUST-2, CTF-HUST-3 and CTF-HUST-4
-1
g , respectively. These values are among the highest reported for
porous organic materials. To our knowledge, the photocatalytic
activity of CTF-HUST-2 is the highest reported for CTFs to date
and higher than reported for COF materials with more crystalline
structures,[4e, 4g] although it must be stated here that these rates
depend strongly on the specific set up used for the photolysis.
Nonetheless, with that caveat, the hydrogen evolution of CTF-
HUST-2 is higher than amorphous CTFS10 (2000 µmol h-1 g ),
-1
[16c]
a crystalline hydrazone-based COF, TFPT-COF (1970 µmol h g-
-
1
1)[4e]
and azine-based N
- COF (1703 µmol h-1 g )[4g].The H
-1
3
2
(
Scheme 1c-1e) were also observed by experiment (see shoulder
production rates of theses CTF-HUST materials are also
peaks in Figure 2b), although these materials are only partially
ordered, and a distribution of pore sizes is often observed in
purely amorphous porous polymers.[7d] Similarly, such peaks can
be artifacts of the NL-DFT analysis. We further investigated the
carbon dioxide and hydrogen adsorption properties of these CTF-
HUSTs (Figure 2c-2d and Figure S11). CTF-HUST-2 has the
highest hydrogen uptake in this series (1.30 wt% at 1.00 bar and
comparable with graphitic carbon nitrides, such as mpg-C
3
N
4
-
-1
-1
(1490 µmol h
g ) and crystalline PTI nanosheets (1750 µmol h
1
-1 [16c, 16d]
g ).
The high photocatalytic activity could be attributed to
in part to the layered structures, which may be beneficial for
photocatalysis because the thin layers could shorten the
migration of generated charges and suppress the charge
recombination. The stability of the CTF-HUST-2 photocatalyst
was also studied. Photocatalytic hydrogen evolution could be
observed for CTF-HUST-2 more than 5 times without any obvious
loss of activity over a total of 15 h irradiation time (Figure 3f).
Besides potential applications in photocatalysis, layered
materials have also been explored extensively for energy storage,
for example carbonaceous layered materials have been studied
7
(
7 K, Figure 2c) and CTF-HUST-3 has the highest CO
13.8 wt% at 273 K, Figure 2d). The isosteric heat of adsorption
was also calculated from the CO isotherms measured at 273 K
and 298 K (Figure S11b).At the onset of adsorption, the heat of
was 30, 29, 33 and 32 kJ mol−1 for CTF-HUST-
adsorption of CO
, CTF-HUST-2, CTF-HUST-3, and CTF-HUST-4, respectively
2
uptake
2
2
1
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COMMUNICATION
In summary, we have developed a new strategy to construct
covalent triazine frameworks by
a novel polycondensation
reaction under mild, potentially scalable conditions, avoiding high
reactions temperatures or strong acids. Four layered CTF-HUST
materials with different building blocks and geometries were
prepared. The CTF-HUSTs displayed good performance in gas
adsorption, photocatalysis and, after pyrolysis, in sodium-ion
battery applications. These findings provide a novel strategy for
the design and synthesis of new classes of robust, functional
earth-abundant CTF materials for a variety of processes in energy
storage, energy production and separation.
Acknowledgements
We thank the Analysis and Testing Center, Huazhong University
of Science and Technology for assistance in the characterization
of materials. This work was financially supported by funding from
National Natural Science Foundation of China (Grant No.
Figure 3. (a) UV-Visible spectra of CTF-HUST-1 (black), CTF-HUST-2(red),
CTF-HUST-3(blue) and CTF-HUST-4(magenta) in the solid state; Solid state
image of (b) CTF-HUST-1, (d) CTF-HUST-2, (d) CTF-HUST-3 and (e) CTF-
21474033, 21604028, 21673087 and T21474033), the
2
HUST-4; (f)Time course of H evolution of CTF-HUST-1(black curve), CTF-
HUST-2 (red curve), CTF-HUST-3 (blue curve) and CTF-HUST-4 (magenta
curve) (>420 nm) and stability test for CTF-HUST-2 for running over 5 times; g)
H evolution rate of CTF-HUSTs.
2
International S&T Cooperation Program of China (Grant No.
2016YFE0124400), and the Program for HUST Interdisciplinary
Innovation Team (Grant No. 2016JCTD104). We thank EPSRC
for funding (EP/N004884/1).
as anode materials for lithium-ion battery (LIBs) or sodium-ion
battery (SIBs).[17] Sodium-ion battery is a promising alternative to
lithium-ion battery because sodium has lower cost and is more
abundant. However, because sodium ion has a larger space than
lithium, the interlayer distance is important for an effective
electrode materials in SIBs. For example, graphite has been
commercially available as Li-ion batteries, however, it cannot
work as efficient SIB anode materials because of the small
interlayer distance that impedes the insertion and extraction of
sodium ions.[18] Recently, a COF derived N-doped carbonaceous
Keywords: covalent triazine frameworks• layered materials •
gas adsorption • photocatalysis• energy storage
[1]
a) A. P. Côté, A. I. Benin, N. W. Ockwig, M. O'Keeffe, A., J. Matzger, O.
M. Yaghi, Science 2005, 310, 1166–1170; b) J. W. Colson, A. R. Woll, A.
Mukherjee, M. P. Levendorf, E. L. Splitler, V. B. Shields, M. G. Spencer,
J. Park, W. R. Dichtel, Science 2011, 332, 228–231; c) X. Feng, X. Ding,
D. Jiang, Chem. Soc. Rev. 2012, 41, 6010–6022; d) S-Y. Ding, W. Wang,
Chem. Soc. Rev. 2013, 42, 548–568; e) B. P. Biswal, S. Chandra, S.
Kandambeth, B. Lukose, T. Heine, R. Banerjee, J. Am. Chem. Soc. 2013,
135, 5328–5331; f) Q. Fang, Z. Fang, S. Gu, R. B. Kaspar, J. Zheng, J.
Wang, S. Qiu, Y. Yan, Nat. Commun. 2014, 5, 1; g) T-Y. Zhou, S-Q. Xu,
Q. Wen, Z-F. Pang, X. Zhao, J. Am. Chem. Soc. 2014, 136, 15885–
material was reported to work as efficient anode materials in
SIBs.[19] Inspired by the layer structures, we performed the
pyrolysis of the CTF-HUSTs (p-CTF-HUSTs) and characterized
the resulting materials (Figure S12). p-CTF-HUST-4 has a largest
interlayer distance of 3.9 Å in the series (Figure S12d). It is known
that a minimum 3.7 Å interlayer distance is required for an
effective sodium transportation for a SIBs.[18] Therefore, p-CTF-
HUST-4 is promising candidates for SIBs. We further observed
the AFM images of these pyrolyzed CTFs and found that p-CTF-
HUSTs also have layered structures after pyrolysis, which may be
either due to the preexisting layered structures or subsequent
graphitization of the materials during pyrolysis (Figure S13). As a
proof of concept, we thereby tested p-CTF-HUST-4 as an anode
material for SIBs. It was found that p-CTF-HUST-4 exhibited high
reversible capacity and excellent cycling and rate performances.
A relatively small irreversible capacity was observed within the
15888; h) P. J. Waller, F. Gándara, O. M. Yaghi, Acc. Chem. Res. 2015,
48, 3053–3063; i) G. Lin, H. Ding, D. Yuan, B. Wang, C. Wang, J. Am.
Chem. Soc. 2016, 138, 3302–3305.
[2]
a) H. Furukawa, O. M. Yaghi, J. Am. Chem. Soc. 2009, 131, 8875–8883;
b) C. J. Doonan, D. J. Tranchemontagne, T. G. Glover, J. R. Hunt, O. M.
Yaghi, Nat. Chem. 2010, 2, 235–238.
[3]
a) S-Y. Ding, J. Gao, Q. Wang, Y. Zhang, W. G. Song, C-Y. Su, W. Wang,
J. Am. Chem. Soc. 2011, 133, 19816–19822; b) A. Nagai, X. Chen, X.
Feng, X. Ding, Z. Guo, D. Jiang, Angew. Chem. Int. Ed. 2013, 52, 3770–
3
774; Angew. Chem. 2013, 125, 3858–3862; c) P. Pachfule, S.
Kandambeth, D. D. Díaz, R. Banerjee, Chem. Commun. 2014, 50, 3169-
172.
3
[4]
a) E. L. Spitler, W. R. Dichtel, Nat. Chem. 2010, 2, 672–677; b) E. L.
Spitler, J. W. Colson, F. J. Uribe-Romo, A. R. Woll, M. R. Giovino, A.
Saldivar, W. R. Dichtel, Angew. Chem. Int. Ed. 2012, 51, 2623–2627;
Angew. Chem. 2012, 124, 2677–2681; c) X. Ding, L. Chen, Y. Honsho,
X. Feng, O. Saengsawang, J. Guo, A. Saeki, S. Seki, S. Irle, S. Nagase,
V. Parasuk, D. Jiang, J. Am. Chem. Soc. 2011, 133, 14510–14513; d) M.
Dogru, M. Handloser, F. Auras, T. Kunz, D. Medina, A. Hartschuh, P.
Knochel, T. Bein, Angew. Chem. Int. Ed. 2013, 52, 2920–2924; Angew.
Chem. 2013, 125, 2992–2996; e) L. Stegbauer, K. Schwinghammer, B.V.
Lotsch, Chem. Sci. 2014, 5, 2789−2793; f) S. Lin, C. S. Diercks, Y. B.
Zhang, N. Kornienkol, E. M. Nichols, Y. Zhao, A. R. Paris, D. Kim, P.
+
voltage range 0.05–2.0 V (vs. Na/Na ). As shown in Figure S14a,
-1
the initial discharge capacity was 467 mAh g , which compares
favorably with lithium-ion battery performance,[20] although many
other factors such as volumetric capacity, potential of reaction,
and charge/discharge rates are also important for real devices.
The material also shows high coulombic efficiency, rate
performance and stability (Figure S14b-d).
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Yang, O. M. Yaghi, C. J. Chang, Science 2015, 349, 1208-1213; g) V. S.
Vyas, F. Haase, L. Stegbauer, G. Savasci, F. Podjaski, C. Ochsenfeld,
B.V. Lotsch, Nat. Commun. 2015, 6, 8508.
[5]
a) P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem. Int. Ed. 2008, 47,
450–3453; Angew. Chem. 2008,120, 3499 – 3502; b) M. J. Bojdys, J.
3
Jeromenok, A. Thomas, M. Antonietti, Adv. Mater. 2010, 22, 2202–2205.
N. A. Zwaneveld, R. Pawlak, M. Abel, D. Catalin, D. Gigmmes, B. Denis,
L. Porte, J. Am. Chem. Soc. 2008, 130, 6678–6679.
[
6]
7]
[
a) S. Ren, M. J. Bojdys, R. Dawson, A. Laybourn, Y. Z. Khimyak, D. J.
Adams, A. I. Cooper, Adv. Mater. 2012, 24, 2357–2361; b) X. Zhu, C.
Tian, S. M. Mahurin, S-H Chai, C. Wang, S. Brown, G. M. Veith, H. Luo,
H. Liu, S. Dai, J. Am. Chem. Soc. 2012, 134, 10478–10484; c) C. E.
Chan-Thaw, A. Villa, P. Katekomol, D. Su, A. Thomas, L. Prati, Nano Lett.
2
010, 10, 537–541; d) L. Hao, J. Ning, B. Luo, B. Wang, Y. Zhang, Z.
Tang, J. Yang, A. Thomas, L. Zhi, J. Am. Chem. Soc. 2015, 137, 219–
25; e) R. Palkovits, M. Antonietti, P. Kuhn, A. Thomas, F. Schüth,
Angew. Chem. Int. Ed. 2009, 37, 6909-6912; Angew. Chem. 2009, 121,
2
7042–7045; f) H. Liao, H. Ding, B. Li, X. Ai, C. Wang, J. Mater. Chem. A
2014, 2, 8854–8858; g) K. Schwinghammer, S. Hug, M. B. Mesch, J.
Senker, B. V. Lotsch, Energy Environ. Sci. 2015, 8, 3345–3353.
a) R. S. Sprick, J-X. Jiang, B. Bonillo, S. Ren, T. Ratvijitvech, P. Guiglion,
M. A. Zwijnenburg, D. J. Adams, A. I. Cooper, J. Am. Chem. Soc. 2015,
[8]
137, 3265-3270; b) B. Bonillo, R. S. Sprick, A. I. Cooper, Chem. Mater.
2016, 28, 3469–3480; c) R. S. Sprick, B. Bonillo, M. Sachs, R. Clowes,
J. R. Durrant, D. J. Adams, A. I. Cooper, Chem. Commun. 2016, 52,
0008-10011.
S. Biswas, S. Batra, Eur. J. Org. Chem. 2012, 3492-3499.
1
[
[
9]
10] K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A. Pierotti, J.
Rouquérol, T. Siemieniewska, Pure & Appl. Chem. 1985, 57, 603–619.
11] Y. Zhao, K. X. Yao, B. Teng, T. Zhang, Y. Han, Energy Environ. Sci. 2013,
[
[
6, 3684–3692.
12] a) M. G. Rabbani, H. M. El-Kaderi, Chem. Mater. 2011, 23, 1650–1653;
b) M. G. Rabbani, T. E. Reich, R. M. Kassab, K. T. Jackson, H. M. El-
Kaderi, Chem. Commun. 2012, 48, 1141–1143; c) M. G. Rabbani, H. M.
El-Kaderi, Chem. Mater. 2012, 24, 1511–1517.
[13] P. Mohanty, L. D. Kull, K. Landskron, Nat. Commun. 2011, 2, 401.
[14] R. Dawson, D. J. Adams, A. I. Cooper, Chem. Sci. 2011, 2, 1173–1177.
[15] Y. Luo, B. Li, W. Wang, K. Wu, B. Tan, Adv. Mater. 2012, 24, 5703–5707.
[16] a) S. Kuecken, A. Acharjya, L. J. Zhi, M. Schwarze, R. Schomacker and
A. Thomas, Chem. Commun., 2017, 53, 5854-5857; b) J. H. Bi, W. Fang,
L. Y. Li, J. Y. Wang, S. J. Liang, Y. H. He, M. H. Liu and L. Wu, Macromol.
Rapid Commun., 2015, 36, 1799-1805; c) L. Y. Li, W. Fang, P. Zhang, J.
H. Bi, Y. H. He, J. Y. Wang, W. Y. Su, J. Mater. Chem. A 2016, 4, 12402-
12406; d) X. Wang, K. Maeda, X. Chen, K. Takanabe, K. Domen, Y. Hou,
X. Fu, M. Antonietti, J. Am. Chem. Soc., 2009, 131, 1680; e) K.
Schwinghammer, M. B. Mesch, V. Duppel, C. Ziegler, J. Senker, B. V.
Lotsch, J. Am. Chem. Soc. 2014, 136, 1730; f) R. S. Sprick, J.-X. Jiang,
B. Bonillo, S. Ren, T. Ratvijitvech, P. Guiglion, M. A. Zwijnenburg, D. J.
Adams, A. I. Cooper, J. Am. Chem. Soc. 2015, 137, 3265; g) R. S. Sprick,
B. Bonillo, R. Clowes, P. Guiglion, N. J. Brownbill, B. J. Slater, F. Blanc,
M. A. Zwijnenburg, D. J. Adams, A. I. Cooper, Angew. Chemie 2016, 128,
1824; Angew. Chem., Int. Ed. 2016, 55, 1792.
[
17] a) A. C. Ferrari, Solid. State Commun. 2007, 143, 47–57; b) Y.
Dall'Agnese, P. L. Taberna, Y. Gogotsi and P. Simon, J. Phys. Chem.
Lett., 2015, 6, 2305-2309; c) Z. G. Luo, J. Zhou, L. R. Wang, G. Z. Fang,
A. Q. Pan and S. Q. Liang, J. Mater. Chem. A, 2016, 4, 15302-15308; d)
L. L. Peng, Y. Zhu, D. H. Chen, R. S. Ruoff and G. H. Yu, Adv. Energy
Mater., 2016, 6,1600025.
[
[
[
18] Y. Wen, K. He, Y. J. Zhu, F. D. Han, Y. H. Xu, I. Matsuda, Y. Ishii, J.
Cumings, C. S. Wang, Nat. Commun. 2014, 5, 4033.
19] X. J. Zhang, G. Zhu, M. Wang, J. B. Li, T. Lu, L. K. Pan, Carbon, 2017,
1
16, 686-694.
20] R. Raccichini, A. Varzi, S. Passerini, B. Scrosati, Nat. Mater. 2015, 14,
71-279.
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Angewandte Chemie International Edition
10.1002/anie.201708548
COMMUNICATION
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COMMUNICATION
A new strategy was developed to
construct CTFs by a polyconden-
sation approach. It allows the
synthesis of CTFs under mild
conditions from a wide array of
building blocks. The resulting
CTFs present a new type of
layered material with potential
applications in separations,
photocatalysis, and energy
storage.
Kewei Wang, Li-Ming Yang, Xi
Wang, Liping Guo, Guang Cheng,
Chun Zhang, Shangbin Jin,* Bien
Tan,* and Andrew Cooper
Page No. – Page No.
Covalent Triazine Frameworks via
a Low Temperature Poly-
condensation Approach
This article is protected by copyright. All rights reserved.