Crystalline Covalent Triazine Frameworks by In Situ Oxidation of Alcohols to Aldehyde Monomers

Article abstract of DOI:10.1002/anie.201806664

Covalent triazine frameworks (CTFs) with aromatic triazine linkages have recently received increasing interest for various applications because of their rich nitrogen content and high chemical stability. Owing to the strong aromatic C=N bond and high chemical stability, only a few CTFs are crystalline, and most CTFs are amorphous. Herein we report a new general strategy to give highly crystalline CTFs by in situ formation of aldehyde monomers through the controlled oxidation of alcohols. This general strategy allows a series of crystalline CTFs with different monomers to be prepared, which are shown to have higher thermal stability and enhanced performance in photocatalysis as compared with the less crystalline or amorphous CTFs. This open-system approach is very simple and convenient, which presents a potential pathway to large-scale industrial production of crystalline CTFs.

Full text of DOI:10.1002/anie.201806664

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Accepted Article
Title: Crystalline Covalent Triazine Frameworks by In-situ Oxidation of
Alcohols to Aldehyde Monomers
Authors: Manying Liu, Qi Huang, Shaolei Wang, Ziyong Li, Buyi Li,
Bien Tan, and Shangbin Jin
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Crystalline Covalent Triazine Frameworks by In-situ Oxidation of
Alcohols to Aldehyde Monomers
Manying Liu, [a] Qi Huang, [a] Shaolei Wang, [a] Ziyong Li, [b] Buyi Li, [c] Shangbin Jin,* and Bien Tan,*
[a]
[a]
Abstract: Covalent triazine frameworks (CTFs) with aromatic triazine
linkages have recently received increasing interest for various
applications because of rich nitrogen content and high chemical
stability. Due to the strong aromatic C=N bond and high chemical
stability, only a few CTFs are crystalline, and most CTFs are
amorphous. Herein we report a new general strategy to achieve highly
crystalline CTFs by in-situ formation of aldehyde monomers through
the controlled oxidation of alcohols. This general strategy allows to
create a series of crystalline CTFs with different monomers, which are
shown to have higher thermal stability and enhanced performance in
photocatalysis as compared with the less crystalline or amorphous
CTFs. This open system approach is very simple and convenient,
and only limited CTFs by this method possess crystalline
structures. The other effective approach is interfacial
polymerization that can access CTFs with ordered lattice
structures.[
8c, 8l]
However, this method is restricted to the
requirement of monomers dissolving in CH
CTFs synthesized by Friedel–Crafts reaction,
2
Cl
2
. While the other
and superacid
[12]
catalyzed reaction[8b, 8d] are usually completely amorphous. We
have recently developed a polycondensation method to prepare
CTFs, which enriched the tool-box of building blocks and
extended the structural design and diversity in our previous work,
but the obtained CTFs are still mainly amorphous.[8n] Therefore it
is still challenging to synthesize crystalline CTFs.
which presents
a
potential pathway to large-scale industrial
Recently, a mechanism study suggested that the key to
improving crystallization lies in decreasing nucleation rates and
generation of lower concentration of nuclei.[13] According to this
principle, we assume that one may develop a general improved
production of crystalline CTFs.
As an ordered crystalline material, covalent organic frameworks
crystallization strategy for CTFs, in which the nucleation rates can
(
COFs) have become very popular and thus received enormous
[14]
be controlled. According to the literatures,
alcohols can
attention in recent decades because the structure of COFs can
be determined precisely.[ A lot of efforts have been devoted to
obtain high quality COFs crystals, such as choosing solvents
gradually be oxidized to aldehydes in the presence of air in
dimethyl sulfoxide (DMSO). Therefore, we designed a novel
strategy to achieve highly crystalline CTFs by slowing down the
nucleation process through in-situ formation of aldehyde
monomers by controlled oxidation of alcohol monomers in an
open system in the polycondensation reaction (Scheme 1).
According to this strategy, a series of crystalline CTFs, i.e., CTF-
C1, CTF-C2 and CTF-C3 were successfully prepared.
1]
[
1a, 2]
[3]
carefully,
addition of acidic catalysts,
π-electronic
O.[6] The
[
4]
[5]
interactions, molecular docking sites, and adding H
2
stronger the bonds, the harder it is to crystallize in the reversible
reactions.[1b, 7] Therefore, the preparation of crystallized COFs
with strong covalent bonds, especially aromatic C=N bonds, is still
a formidable challenge.
Covalent triazine frameworks (CTFs) with aromatic triazine
linkages have received increasing interest for many applications
The alcohol oxidation strategy in this study, to the best of our
knowledge, is the first try on synthesizing crystalline covalent
organic frameworks in an open system. This approach is very
simple and convenient to prepare crystalline CTFs. Most
importantly, it is a general and non-carbonized method compared
[
8a-8b, 8d-8g]
[8c, 8i-8l, 8o-
in gas adsorption and storage,
energy storage,
8p]
heterogeneous catalysis[8q-8r] and photocatalysis[8h, 8m-8n] due to
high nitrogen content and high chemical stability. Enhanced
crystallinity can improve charge transport in the framework, which
is beneficial to photoelectric properties.[ However, due to the
strong aromatic C=N bond, only a few CTFs are crystalline.
Thomas and coworkers found that ionthermal synthesis in a
sealed ampoule at high temperature (≥400 °C) can achieve few
[8a, 8e, 10-11]
to high temperature methods.
To demonstrate the alcohol oxidation strategy, we designed a
model experiment and replaced double-functional monomers with
mono-functional monomers to simplify the reaction system under
similar polymerization conditions (see Section 2 in the Supporting
9]
Information (SI)). Alcohols can be oxidized to aldehydes slowly in
[
8a, 8e, 10]
[11]
crystalline CTFs.
Recently, Baek et al
developed a
the DMSO solution.[
14]
We also found the formation of
novel synthesis strategy for CTFs using phosphorus pentoxide as
a catalyst at high temperature (≥400 °C). But these methods
usually cause partial carbonization because of high temperature
benzaldehyde by high performance liquid chromatography
HPLC) (Figure S1). From FT-IR spectra of the products collected
(
at different time intervals in the model reaction (Figure 2b), the
relative intensity of characteristic vibration peaks of triazine
groups (C=N and C-N) gradually increased with the reduction of
alcohol groups (C-O and O-H), which indicate that benzyl alcohol
is not immediately oxidized to aldehyde but is slowly oxidized to
aldehyde, and the oxidation reaction run through the whole
polymerization process.
To further demonstrate our strategy, we designed a series of
control experiments for CTF-C1 (see Section 2 and Table S1 in
SI). By increasing the temperature to 180 °C for 36 h directly, only
some soluble oligomers or fragments were formed (Figure S3).
By performing the polymerization reaction at lower temperature
[
a]
M. Liu, Q. Huang, S. Wang, Prof. S. Jin, Prof. B. Tan
Key Laboratory of Material Chemistry for Energy Conversion and
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
Dr. Z. Li
Department College of Food and Drug, Luoyang Normal University,
Luoyang 471934, PR (China)
Dr. B. Li
[
[
b]
c]
Department of Chemistry and Materials Innovation Factory,
University of Liverpool, Crown Street, Liverpool, L69 7ZD (UK).
(
100 °C) however, mainly yielded low degree of crystalline CTFs
Supporting information for this article is given via a link at the end of
the document.
even after 24 h (Figure S2aI). It may be due to the fact that high
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Figure 1. (a) FT-IR spectrum and (b) Solid state 13C CP-MAS NMR of CTF-
C1 (black), CTF-C2 (blue) and CTF-C3 (cyan).
Similarly, the chemical shift at 168.6 ppm for CTF-C2 and CTF-
C3 are in line with CTF-C1. The result also unambiguously
confirmed the formation of triazine units in CTF-C1, CTF-C2 and
CTF-C3. Furthermore, the deconvolution of N1s peaks around
3
98.9 eV for CTF-C1, CTF-C2 and CTF-C3 were all attributed to
pyridine nitrogen(C=N-C) by X-ray photoelectron spectroscopy
XPS) measurement (Figure S10).[8d, 8k] In addition, elemental
(
Scheme 1. (a) The general strategy by slowing down the nucleation
process through in-situ formation of aldehyde monomers by controlled
oxidation of alcohol monomers in an open system. (b) Monomers: BDM
for CTF-C1, NDM for CTF-C2 and BPDM for CTF-C3 respectively.
analysis shows that the carbon and nitrogen contents are close to
the theoretical values (Table S2). In a word, the chemical
composition of the resulting materials also shows the formation of
triazine rings.
Figure 2a shows the X-ray diffraction (XRD) patterns of CTF-
C1 in conjunction with structural simulations. The diffraction
peaks at approximately 7.3°, 12.6°, 14.7° and 26.1° are assigned
to (100), (110), (200) and (001) facets respectively. The simulated
XRD patterns of the resulting model in an eclipsed orientation AA
stacking matched well the experimental data indicating the
formation of crystalline CTFs most likely with an eclipsed AA
structure. In terms of the peak intensity and the number of
exposed peaks, CTF-C1 is better especially than the reported
CTF-HUST-1.[8n] The enhancement of crystallinity for CTFs may
be attributed to the lower reaction rate in initial stage due to slow
generation of aldehydes by controlled oxidation of alcohol, which
enables the generation of low density nuclei to promote crystal
growth.
According to this strategy, the CTF-C2 and CTF-C3 were
designed and synthesized successfully to show the generality of
the method (See Section 2 in SI). Interestingly, both CTFs with
good crystallinity synthesized by alcohol condensation are most
likely AA stacking structures, in consistent with the theoretical
XRD pattern simulated by Materials Studio software (Figure 2b
and 2c, Figure S22-S25). The model structures of CTF-C2 and
CTF-C3 were both constructed with a unit cell with a P6/mmm
space group (Figure S22 and S24). The unit cell parameters of
CTF-C2 are a = b = 26.370 Å, c = 3.400 Å and the unit cell
parameters of CTF-C3 are a = b = 28.300 Å, c = 3.40 Å. To
confirm the simulation of unit cell of CTFs, Pawley refinements
were carried out. The Pawley refinement of CTF-C2 was
successfully done with a refined parameter of Rwp = 2.37% and
Rp = 1.78% and that of a unit cell of CTF-C2 are a = b = 26.316
Å, c = 3.419 Å. The Pawley refinement for CTF-C3 is with a
temperature leads to rapid oxidation of alcohol to form aldehyde,
which generates high concentration of nuclei to form small
particles.[13] While, the initial low temperature is conducive to the
formation of nucleation based on slow oxidation of alcohols. By
subsequently increasing the temperature to 120 °C, 150 °C and
the boiling point (~180 °C), respectively, an increasing crystallinity
trend of CTFs was observed (Figure S2aII - 2aIV). Interestingly,
the BET surface area also gradually increased with an increase
of reaction temperature (Figures S4-S6), and macropores and
mesopores proportion gradually decreased (Figures S7-S9). It
implies that after the formation of nuclei, higher temperature is
beneficial to the crystal growth and micropore formation for CTF-
C1.
Therefore, the reaction rate was retarded and controlled by low
concentration of aldehyde monomers generated from the slow
oxidation of alcohols, so that the nucleation rates slowed down to
generate lower concentration of nuclei. Afterwards, however, an
increase in temperature promoted the crystal growth. Therefore,
it is very important to keep the polymerization reaction at a lower
temperature to control the formation of aldehydes in the initial
stage and then maintain a higher temperature to enhance the
polymerization rate in the second stage to improve the
crystallization of CTFs.
By Fourier-transformed infrared (FT-IR) analysis, the
characteristic vibrations at 1517 cm and 1353 cm−1 were
observed, which indicate the successful formation of the triazine
frameworks for CTF-C1, CTF-C2 and CTF-C3 (Figure 1a).[
On solid state 13C CP/MAS spectra (Figure 1b), the observed
chemical shifts at 127.7 ppm and 137.4 ppm can be assigned to
the phenyl carbons and the chemical shift at 168.6 ppm is
ascribed to the carbon signal from triazine rings for CTF-C1.[8i, 15]
−1
8i, 8n]
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synthesized by this general approach have some common
characteristics such as AA stacking structures, high surface area
and similar layer morphologies. These crystalline CTF
nanosheets may have good applications in photocatalysis
because of the good crystallinity and high surface area.
Due to better crystalline properties, we set out to investigate the
photophysical applications of CTFs. The photocatalytic properties
of newly synthesized CTF-Cs were evaluated in sacrificial
photocatalytic hydrogen evolution under visible light irradiation
(
>420 nm). The results revealed that the hydrogen evolation rates
-
1 -1
of CTF-C1, CTF-C2 and CTF-C3 were 5100 μmol h g , 2400
μmol h-
1
-1
-1 -1
g and 650 μmol h g , respectively (Figure 3a). Among
the CTFs, CTF-C1 has a significant high photocatalytic hydrogen
evolution rate, which is much higher than previously reported
[
8n]
CTF-HUST-1
and other similar porous materials such as
CTFs[ and COFs.[18] The recyclability of these CTFs was also
examined by measuring photocatalytic hydrogen evolution over 5
times. It was observed that the photocatatic hydrogen evolution
rate could approach up to 3880 μmol h-1 g-1 over a total of 25 h
irradiation time (Figure 3b).
17]
We recorded the optical absorption properties of these CTF-Cs
samples by measuring UV-visible spectra and found that they
could absorb a wide range of visible light up to around 850 nm
(
Figures S17 - S19). The optical photographs of solid state CTF-
Cs showed that they are yellowish powders, which are in line with
their absorption properties. Electrochemical impedance
spectroscopy (EIS), and photocurrent measurements were
carried out to understand the enhancement of the photocatalytic
activity. Photocurrent measurements showed a fast photocurrent
response in all of the electrodes under visible light upon each
switch-on and switch-off event (Figure 3d). The photocurrent of
crystalline CTF-C1 is higher than amorphous CTF-HUST-1, which
is in good agreement with the photocatalytic activities. The EIS
arc size of crystalline CTF-C1 is smaller than that of the
amorphous CTF-HUST-1, indicating that the charge transport in
Figure 2. Experimental (red) and simulated AA stacking (blue) XRD
patterns, difference plot (experimental, refined, black) and top and side
views eclipsed (AA) structures of (a) CTF-C1, (b) CTF-C2 and (c) CTF-C3.
Inset shows the top and side views of eclipsed (AA) structures. (d) N
2
adsorption (closed circles) and desorption (open circles) isotherms (77 K) of
CTF-C1 (black), CTF-C2 (blue) and CTF-C3 (cyan). Notes: Vertically offsets
3
-1
3
-1
values a) 200 cm g for CTF-C2 and 400 cm g for CTF-C3.
refined parameter of Rwp = 2.13% and Rp = 1.61% and that of a
unit cell of CTF-C3 are a = b = 28.381 Å, c = 3.417 Å. These
results indicate that the difference between the diffraction peaks
of simulation and experimental are almost negligible.
The thermal gravimetric analysis (TGA) measurements reveal
o
that CTF-C1, CTF-C2 and CTF-C3 are stable up to 650 C, 650
oC and 600 oC without significant loss of mass (Figure S12),
showing their better stability than that of amorphous CTFs.[
8n, 16]
The porous structure of CTFs were characterized by
N
2
adsorption−desorption measurements at 77 K. They showed
typical type-IV reversible isotherms, indicating the presence of
micropores and mesopores. The Brunauer–Emmett–Teller (BET)
2
-1
surface area of CTFs were calculated to be 599 m g for CTF-
2
-1
2
-1
C1, 520 m g for CTF-C2 and 598 m g for CTF-C3 (Figure 2d).
From the pore size distribution, the characteristic pore sizes are
in agreement with the pore sizes calculated from the optimized
model, i.e., 1.2 nm, 1.22 nm and 1.27 nm for CTF-C1, CTF-C2
and CTF-C3, respectively (Figure S13). However, it should be
noted that these observed micropores size around 0.5~0.7 nm in
the pore size distribution probably point to the defects formation.[
The morphologies for CTF-C1, CTF-C2 and CTF-C3 probed by
scanning electron microscope (SEM) show that these CTFs
consist of nanomaterials without specific morphological features
1i]
Figure 3. (a) Time course of photocatalytic hydrogen evolution for CTF-
C1 (red curve), CTF-C2 (black curve) and CTF-C3 (blue curve)
respectively (>420 nm), (b) Recyclability of CTF-C1 for 5 cycles over 25 h,
(Figure S14 - S17). From TEM images (Figures S11a - S11c) and
(
c) EIS Nyquist plots and (d) Photocurrent response of the reported CTF-
[8n]
AFM images (Figures S11d – S11f), the layered morphologies of
CTF-C1, CTF-C2 and CTF-C3 are obvious. Therefore, the CTFs
HUST-1 and CTF-C1. The error bar represents the standard deviation
from three experimental trial.
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CTF-C1 is better than CTF-HUST-1, which is beneficial to
enhance their photocatalytic performance (Figure 3c). Therefore,
the improvement of photocatalytic performance may be attributed
to better charge transport ability and broader light absorption
because of higher crystallinity of CTFs.
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strategy to prepare a series of highly crystalline CTF-Cs by using
alcohol monomers to evolve into aldehydes, where the reaction
rates were controlled by gradually generating aldehydes by in-situ
slow oxidation of alcohols. The crystalline CTFs showed much
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Angewandte Chemie International Edition
10.1002/anie.201806664
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Covalent triazine frameworks
were synthesized by in-situ
formation of aldehyde
monomers by the controlled
oxidation of alcohols in an
open system. This approach
is very simple, convenient
and general.
M. Liu, Q. Huang, S.Wang,
Z. Li, B. Li, S.Jin,* B. Tan,*
Crystalline Covalent Triazine
Frameworks by In-situ
Oxidation of Alcohols to
Aldehyde Monomers
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