Two-dimensional crystalline covalent triazine frameworksviadual modulator control for efficient photocatalytic oxidation of sulfides

Article abstract of DOI:10.1039/d1ta03951b

Two-dimensional crystalline covalent triazine frameworks (2D-CTFs) are emerging 2D materials with the characteristics of fully annulated conjugated structures and aromatic nitrogen-rich skeletons. Due to the difficulty in the control of the polymerization

Full text of DOI:10.1039/d1ta03951b

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Materials Chemistry A
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Two-dimensional crystalline covalent triazine
frameworks via dual modulator control for efficient
photocatalytic oxidation of sulfides†
Cite this: J. Mater. Chem. A, 2021, 9,
6405
1
a
a
c
a
a
c
Xuepeng Wang,‡ Siquan Zhang,‡ Xia Li, Zhen Zhan, Bien Tan, Xianjun Lang
ab
and Shangbin Jin
*
Two-dimensional crystalline covalent triazine frameworks (2D-CTFs) are emerging 2D materials with the
characteristics of fully annulated conjugated structures and aromatic nitrogen-rich skeletons. Due to the
difficulty in the control of the polymerization dynamics, the preparation of crystalline 2D-CTFs is still
a daunting challenge compared to that of other organic framework materials. Herein, we report the
construction of crystalline 2D-CTFs using dual modulator control, in which aniline and a co-solvent are
used as dual modulators for a dynamic covalent linkage formation and non-covalent self-assembly
process, respectively. The strategy successfully leads to crystalline CTFs from different functional
building blocks. The crystalline CTFs could be further regulated via peripheral functionalization, which
dramatically boosted the photocatalytic activity for oxidation of sulfides into sulfoxides, and excellent
conversion rates and selectivity for a wide range of sulfides with various functional groups were achieved
after functionalization with methoxyl groups. This work gives new insights into the design and synthesis
of crystalline CTFs for photocatalytic applications.
Received 10th May 2021
Accepted 19th June 2021
DOI: 10.1039/d1ta03951b
rsc.li/materials-a
Crystalline organic frameworks are mainly regulated by the
1
. Introduction
dynamic covalent chemistry via reversible covalent linkages and
33
Two-dimensional (2D) organic crystalline materials, such as 2D self-assembly processes via non-covalent interactions.
covalent organic frameworks (2D-COFs), have attracted enor- According to dynamic covalent chemistry, the reversibility in
mous research attention due to their 2D layered and tailorable the linkage or framework is the essential prerequisite to attain
1
–13
structures.
2D-CTFs, a subtype of 2D-COFs, are built from high crystallinity. Nevertheless, 2D-CTFs have usually suffered
triazine and other aromatic rings, and possess highly stable and from poor reversibility, mainly because of the low reversibility of
annulated porous structures, making them ideal candidates for intermediate bonds in the trimerization or condensation reac-
1
4–17
18–21
22–26
gas adsorption,
heterogeneous catalysis.
crystalline stacking structures and ordered pore structures are their crystallinity, such as monomer concentration control in
photocatalysis,
energy storage,
and tions, as well as the fully conjugated stable frameworks.
27–29
It has been considered that the Although, a variety of strategies have been reported to increase
3
4,35
key advantages of COFs for their functional applications, which the polycondensation reaction,
could provide ordered molecular diffusion or charge transport reaction,
pathways.
However, the crystallinity of the state-of-the-art and microwave-assisted trimerization or other multi-step
D-CTFs remains incomparable with that of 2D-COFs with transformation methods,
interfacial trimerization
36,37
9,38
ionothermal trimerization at high temperatures,
30–32
39,40
2
it is still a challenge to modulate
more reversible linkages, such as boronate-linked or imine- their crystallinity effectively under mild conditions. Recently,
linked 2D-COFs. 2D-CTFs with higher crystallinity are in dynamic control of imine linkage using a modulator has been
demand for advancing their applications.
found very effective to obtain highly crystalline imine-linked
41–44
organic frameworks.
However, the implementation of such
a strategy in 2D-CTFs has been critically challenging due to the
low reversibility and the strict reaction conditions in the
conventional methods. On the other hand, the noncovalent
a
School of Chemistry and Chemical Engineering, Huazhong University of Science and
Technology, Luoyu Road 1037, Wuhan, 430074, China
b
School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xianning interlayer control should be an important part for the genera-
West Road, Xi'an, Shaanxi, 710049, China. E-mail: shangbin@xjtu.edu.cn
tion of crystalline 2D-CTFs, because it may affect the crystal
c
Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences,
growth in the self-assembly process via p–p stacking. However,
Wuhan University, Wuhan 430072, China
it has been paid very little attention and how the crystallinity of
†
1
‡
Electronic supplementary information (ESI) available. See DOI:
0.1039/d1ta03951b
2D-CTFs is affected by the non-covalent approach is unclear. If
we could merge the dynamic covalent chemistry with the non-
These authors contributed equally to this work.
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conditions were named CTF-HUST-d1 and CTF-HUST-e1,
respectively.
The general synthesis procedure was as follows: a mixture of
aldehyde monomer (0.5 mmol), terephthalamidine (1.0 mmol),
Cs CO (2.2 mmol), aniline derivatives (according to actual
2 3
experiments required) and DMSO or other mixed solvents (10
mL) were added into a ask. Then the reaction was heated at
ꢀ ꢀ ꢀ
1
00 C for 24 h, 120 C for 24 h and 160 C for 48 h. Aer cooling
to room temperature, the mixture was washed with DMF and
water. The detailed process can be found in the ESI.†
Scheme 1 Representative schematic view of the dual modulator
control for the synthesis of crystalline 2D-CTFs.
3. Results and discussion
3.1 Aniline and co-solvent dual modulator control
We at rst studied the inuence of the aniline modulators on
the crystallinity. According to the reaction mechanism, the
monofunctional aniline modulators could react with the bisal-
dehyde monomers at the outset. Therefore, the aniline modu-
lators in the polycondensation reaction of CTFs could inhibit
the direct reaction of aldehyde-based monomers with amidine,
and hence may effectively regulate the nucleation and crystal
growth processes of CTFs. We evaluated the anilines which are
incorporated with various substitutional groups, including
aniline, p-toluidine, 2,4,6-trimethylaniline, and 4-bromoani-
line. As shown in Fig. 1a, p-toluidine incorporated with an
covalent self-assembly process, the assessment of higher crys-
talline 2D-CTFs may be possible.
Herein, we report the synthesis of crystalline 2D-CTFs via
a dual modulator control, that is, through dynamic control of
covalent linkage using an aniline modulator and noncovalent
self-assembly regulation using a co-solvent modulator (Scheme
1). The modulation of the reaction dynamics in 2D-CTFs was
realized by using an aniline modulator in the polycondensation
reaction, due to the presence of an intermediate imine-bond
before the cyclization. And the noncovalent modulation was
accomplished by introducing an aromatic co-solvent as
a second modulator to modulate the crystallization process in
CTFs. Assisted by the two modulators, we successfully achieved
electron donating group (–CH ) is proven to be the most effec-
3
ꢀ
tive modulator among the series, and the peak intensity at 7.4
in the PXRD of the CTF sharply increased (blue curve). Aniline
without any substitutional group also works well to enhance the
crystallinity (Fig. 1a, red curve). In contrast, when 4-bromoani-
line incorporated with an electron withdrawing group (–Br) was
used, the crystallinity was not improved (Fig. 1a, purple curve).
Although 2,4,6-trimethylaniline is more electron donating, the
crystallinity of the CTF remains almost unchanged (Fig. 1a,
green curve), which may be related to large steric hindrance in
the structure. These observations indicate that the reactivities
2
D-CTFs with greatly enhanced crystallinity. With the estab-
lishment of this strategy, the crystalline CTFs with variable
structures were shown to achieve high photocatalytic perfor-
mance in the oxidation of suldes, and exhibited excellent yield
and selectivity aer installing electron donating units as the
peripheral side groups in the CTFs' pore walls.
2
. Experimental section
2
.1 Materials
p-Phthalaldehyde, cesium carbonate (Cs
-(hydroxymethyl)benzaldehyde, 2,5-dimethoxyterephthalal-
2
3
CO ), p-phthalaldehyde,
4
dehyde, terephthalamidine, aniline, p-toluidine, 2,4,6-trimethyla-
niline, 4-bromoaniline, toluene, mesitylene, n-hexadecane,
o-dichlorobenzene (o-DCB), benzene-1,4-dicarbonitrile, lithium
bis(trimethylsilyl)amide, N,N-dimethylformamide (DMF), tetrahy-
drofuran (THF) and dimethyl sulfoxide (DMSO) were purchased
from Aladdin Reagent (Shanghai) Co., Ltd.
2.2 Synthesis of CTF materials
The reaction monomers and an aniline modulator were
dispersed in dimethyl sulfoxide (DMSO) and a co-solvent
modulator, and then the mixtures were heated for reaction to
yield the corresponding crystalline CTFs (see the ESI† for the
detailed process). The crystalline CTFs obtained from p-phtha-
laldehyde and 4-(hydroxymethyl)-benzaldehyde are labelled
CTF-HUST-D1 and CTF-HUST-E1, respectively. The products
Fig. 1 Experimental PXRD patterns of the crystalline CTFs: (a) influ-
ence of different aniline modulators, (b) influence of the amount of p-
toluidine (n(NH2) represents the molar amounts of aniline modulators),
(c) the ratio of mixed solvent of DMSO and o-dichlorobenzene (o-
DCB), (d) the crystallinity of CTF-HUST-D1 and CTF-HUST-E1 under
obtained without adding aniline modulators under the same optimal conditions.
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of amino groups in these aniline modulators are crucial to the
dynamic control process and thus have inuence on the crys-
tallinity. This increased crystallinity in the CTFs was indicated
by the increased ordinate peak intensity and the shrunken
background of the PXRD. Due to the competitive reactions,
excess amounts of aniline modulators are needed. We noted
that when the amounts of anilines are three times those of
aldehyde monomers, the optimal result is accomplished in
terms of yield and crystallinity (Fig. 1b, red curve). Too excessive
amounts, however, reduced the yields of CTFs (Fig. 1b, green
Fig. 2 (a) Experimental powder X-ray diffraction patterns of the CTFs
under different conditions. (b) Comparison of the PXRD of CTFs
curve). The CTF-HUST-E1 obtained from the 4-(hydroxymethyl)- synthesized by the present method with that of the CTFs from previous
methods.
benzaldehyde monomer (with a single aldehyde group) also
possesses excellent crystallinity when using the same synthesis
conditions (Fig. 1d and S1b–d†). However, when 1,4-benzene-
dimethanol (without the aldehyde group) was used as the peak at 7.4 in PXRD were increased by nearly two times. These
ꢀ
monomer under the same conditions, the corresponding CTF results indicate that the present strategy is more effective than
34,35
cannot be obtained. This phenomenon implies that the alde- the previous methods.
hyde group is indispensable in this strategy.
Aer investigation of the aniline modulators for the dynamic 3.2 Structural characterization
covalent process, we next explored the inuence of the non-
The resulting crystalline 2D-CTFs were unambiguously charac-
covalent process on the crystallinity. Solvents play an impor-
terized. Fourier-transformed infrared (FT-IR) spectra were
recorded to characterize the CTFs' structures. The characteristic
45–47
tant role in accessing crystalline COFs.
The use of the
solvent effect is also an important way to access noncovalent
À1
À1
peaks at 1518 cm
(–C]N–) and 1352 cm
(–C–N])
48,49
self-assembly systems.
To our surprise, the inuence of the
belonging to the triazine moiety in CTF-HUST-D1 and CTF-
solvent effect has been rarely explored in CTFs. In previous
studies of CTFs synthesized by the polycondensation reaction,
only a single solvent has been used, where DMSO works as the
50
HUST-E1 are in line with previous work (Fig. 3a). The char-
acteristic chemical shi of the triazine carbon atom is at
1
70 ppm and the assignment of the other carbon atoms as
34,35,50,51
sole reaction medium as well as the oxidant.
DMSO is
13
shown in the solid-state C NMR spectra can also conrm the
desired structures (Fig. 3b). Elemental analysis shows that the
carbon, nitrogen and oxygen contents of CTFs are close to the
theoretical values (Table S2†). X-ray photoelectron spectroscopy
a good solvent for monomers and oligomers because of its high
polarity. We assumed that the combination of DMSO solvent
with non-polar solvents, particularly aromatic solvents, may be
able to control the self-assembly process in the crystallization of
(XPS) revealed the bonding type of each element in CTFs. As
2D-CTFs. Various aromatic or nonpolar organic solvents,
shown in Fig. 3c and d, the high-resolution C 1s and N 1s
surveys of CTF-HUST-D1 and CTF-HUST-E1 display peaks at
including toluene, mesitylene, o-dichlorobenzene (o-DCB), or n-
hexadecane, were hence adopted as the co-solvent. We found
that mesitylene, o-DCB and n-hexadecane are benecial for the
generation of higher crystallinity. Among them, the combina-
tion of DMSO with o-DCB gives the most positive result
2
87.3 eV and 399.2 eV, which are assigned to C]N–C of the
51
triazine moiety. The peaks were tted with a single peak,
(Fig. S1a†). We further revealed that the solvent ratio is critical
to the crystallinity, and the highest crystallinity of CTF-HUST-
D1 is achieved when the volume ratio of DMSO/o-DCB is 1 : 3
(Fig. 1c, green curve). The reason for the enhanced crystallinity
may be due to that the solvents of low polarities are conducive to
the assembly of the monomers or oligomers (nucleus) in the
52
crystallization, and thereby are capable of modulating the
crystal growth in a much ordered manner.
As shown in Fig. 2a, aer adding p-toluidine and a co-solvent
as dual modulators, the crystallinities of CTF-HUST-D1 and
CTF-HUST-E1 were signicantly enhanced, which is clearly
ꢀ
evidenced by the prominently enhanced peak intensity at 7.4
and their narrowed half-width. By comparing the full width at
ꢀ
half maxima (FWHM) of the peak at 7.4 in PXRD patterns with
those of the previously reported CTF-HUST-HC1 (FWHM: 1.91)
and CTF-HUST-C1 (FWHM: 1.67) measured under the same
conditions (Fig. 2b and Table S1†), the FWHM of the peaks in
CTF-HUST-D1 (FWHM: 1.52) and CTF-HUST-E1 (FWHM: 1.45)
13
Fig. 3 FT-IR spectra (a), solid-state CNMR spectra (b), high-resolu-
tion XPS C 1s and N 1s spectra (c and d) for CTF-HUST-D1 and CTF-
were obviously narrowed. Furthermore, the intensities of the HUST-E1.
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indicating the lesser defective structures formed in this into the aldehyde monomer (Fig. 4a, b and S6–S10†). Indeed,
strategy. CTF-HUST-D2 showed a much higher conversion rate of 55%
The morphologies of CTFs were investigated by scanning than CTF-HUST-D1 (13%) within a short interval of 30 min.
electron microscopy (SEM). Compared with CTF-HUST-d1 and Aer extension of the reaction time, excellent conversion rate of
CTF-HUST-e1 that are synthesized only using DMSO solvent in suldes and selectivity to products were successfully achieved.
the absence of aniline modulators, CTF-HUST-D1 and CTF- As shown in Table 1, the highest conversion rate up to 99% and
HUST-E1 synthesized from the mixed solvent system (DMSO selectivity up to 96% were obtained within 2 h. The catalytic
and o-DCB) comprise much larger particle sizes (Fig. S2a–e†). reaction also showed a wide generality of sulde substrates,
This implies that the crystal growth is more favored when the indicating that it is an efficient photocatalyst with wide
12,13
competitive reaction occurs with aniline modulators. By versatility.
nitrogen sorption–desorption tests, the Brunauer–Emmett–
Teller (BET) surface areas for CTF-HUST-D1 and CTF-HUST-E1
3
.4 Mechanism of the photocatalytic oxidation
2
À1
are calculated to be 477 and 428 m
g , respectively. The
The photocatalysis mechanism of the CTF was next probed.
average pore size distribution of CTF-HUST-D1 and CTF-HUST-
E1 is centered at 1.2 nm (Fig. S2c and f†). As shown in Fig. S3,†
the lattice fringes in high resolution-transmission electron
microscopy (HR-TEM) clearly imply ordered structures in the
local area in CTF-HUST-D1 and CTF-HUST-E1, which is also
solid evidence for the crystalline structures. TEM-mapping Entry Substrate
demonstrated that the carbon and nitrogen elements are
distributed evenly in the entire CTFs (Fig. S4†). Thermogravi-
Quenching experiments by employing different scavengers were
Table 1 Photocatalytic oxidation of sulfides into sulfoxides by CTF-
a
HUST-D2
b
b
Product
T (h) Conv. (%) Sel. (%)
1
1.1
1.0
91
94
94
95
metric analysis showed that CTF-HUST-D1 and CTF-HUST-E1
ꢀ
are thermally stable until 500 C (Fig. S5†).
2
3.3 Photocatalytic oxidation of suldes
In the previous studies, Wang and coworkers have shown that
crystalline COFs are promising platforms for photocatalytic
12,13
3
4
5
6
7
1.2
1.6
1.4
1.5
1.9
90
92
93
91
91
91
94
96
94
92
selective aerobic oxidation of organic suldes.
With the
establishment of the above strategy, we explored the photo-
catalytic applications of the resulting CTFs in this oxidation
reaction. As shown in Table S3,† the initial test shows that CTF-
HUST-D1 has an excellent selectivity, whereas only a low
conversion rate (13%) was found within 30 min. We anticipated
that the increase of electron-rich segments could improve the
53,54
photocatalytic ability,
as it is more conducive to the gener-
ation of oxidative radical species. Hence, crystalline CTF-HUST-
D2 was designed and synthesized by installing a methoxy group
8
9
2.0
1.4
90
99
94
81
10
1.0
93
85
a
Reaction conditions: sulde (0.5 mmol), CTF photocatalyst
(
0.01 mmol calculated based on the repeating unit), blue LED
b
Fig. 4 (a) The structure and (b) powder X-ray diffraction patterns of
irradiation (3 W Â 4), CH
3
OH (1 mL), air (1 atm). Conversion and
CTF-HUST-D2, (c) time related transient photocurrent response, (d) selectivity to sulfoxides, determined by GC-FID using chlorobenzene
energy level alignments of CTFs calculated from experimental results. as the internal standard.
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performed to identify the active species that played the major selectivity. This work gives some new insights into the synthesis
role in the catalytic process. As shown in Table S4,† when the of crystalline CTFs, and further shows that crystalline CTFs are
reaction was performed in a nitrogen atmosphere, no reaction powerful platforms for photocatalysis applications.
occurred, and when a superoxide radical scavenger (p-BQ) or
electron trapper (AgNO
selectivity to the target product were also remarkably decreased.
3
) was added, the conversion rate and
Conflicts of interest
These results indicate that oxygen is indispensable to the There are no conicts to declare.
À
catalytic reaction and the superoxide radical (cO
2
) generated in
the photocatalytic process is the essential active species for the
reaction. To directly identify the existence of cO2 during pho-
Acknowledgements
À
tocatalysis, in situ ESR tests were performed by employing 5,5- The nancial support from the National Natural Science
dimethyl-1-pyrroline N-oxide (DMPO) as the trapper. As shown Foundation of China (Grant No. 21875078) is greatly acknowl-
À
in Fig. S11,† the characteristic ESR signals of DMPO–cO
2
were edged. We are also grateful for the support from the China
clearly seen for CTF-HUST-D1, CTF-HUST-E1 and CTF-HUST-D2 Postdoctoral Science Foundation (2019M662582). The authors
under visible-light irradiation. Notably, CTF-HUST-D2 displays thank the Analysis and Testing Center of the Huazhong
the strongest response signal under the same conditions, which University of Science and Technology for their support in the
is in line with the photocatalytic results.
characterization.
The electron-donating methoxy group in CTF-HUST-D2
makes its UV/visible absorption red-shied compared to that
of CTF-HUST-D1 (Fig. S12†). It not only makes the CTF exhibit
a wider light response, but also makes the framework more
conducive to the charge carrier photogeneration and transport
Notes and references
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55,56
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As shown in the photoluminescence (PL) spectra
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(
E
(
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À
negative than the reduction potential of O /cO (À0.33 V vs.
2
2
57
NHE), and the photogenerated electrons of CTF-HUST-D2
À
could be more easily captured by the O
2
to generate cO
2
, and
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