Designed Synthesis of a 2D Porphyrin-Based sp2 Carbon-Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis

Article abstract of DOI:10.1002/anie.201902543

The construction of stable covalent organic frameworks (COFs) for various applications is highly desirable. Herein, we report the synthesis of a novel two-dimensional (2D) porphyrin-based sp² carbon-conjugated COF (Por-sp²c-COF), whi

Full text of DOI:10.1002/anie.201902543

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Accepted Article
Title: Designed Synthesis of a 2D Porphyrin-based sp2 Carbon-
conjugated Covalent Organic Framework for Heterogeneous
Photocatalysis
Authors: Cheng Wang, Rufan Chen, Ji-Long Shi, Yuan Ma, Guiqing
Lin, and Xianjun Lang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201902543
Angew. Chem. 10.1002/ange.201902543
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10.1002/anie.201902543
Angewandte Chemie International Edition
ESSAY
Designed Synthesis of a 2D Porphyrin-Based sp2 Carbon-
Conjugated Covalent Organic Framework for Heterogeneous
Photocatalysis
Rufan Chen,[a] Ji-Long Shi,[a] Yuan Ma,[b] Guiqing Lin,[a] Xianjun Lang[a] and Cheng Wang*[a]
Abstract: The construction of stable covalent organic frameworks
(COFs) toward interesting applications is highly desirable. Herein, we
report the designed synthesis of a novel two-dimensional (2D)
porphyrin-based sp2 carbon-conjugated COF (Por-sp2c-COF), which
adopts an eclipsed AA stacking structure with a BET surface area of
689 m2 g-1. Owing to the C=C linkages, Por-sp2c-COF exhibited high
chemical stability under various conditions, even under harsh
conditions such as 9 M HCl and 9 M NaOH solutions. Interestingly,
Por-sp2c-COF can be used as metal-free heterogeneous
photocatalyst for the visible-light-induced aerobic oxidation of amines
to imines. More importantly, in comparison with imine-linked Por-COF,
the inherent structure of Por-sp2c-COF can allow this material have
several advantages as photocatalyst, including reusability and high
photocatalytic performance. This result clearly demonstrated that 2D
sp2 carbon linked COF can provide an interesting platform for
heterogeneous photocatalysis.
such as amide,[9,10] azine,[11] thiazole,[12] and heteroaromatic
dioxin,[13] have been reported. Among these examples, a new
type of olefin-based COFs, which is synthesized through the
Knoevenagel condensation reaction, has gained increasing
attentions recently.[14] For example, Jiang et al. reported that 2D
pyrene-based
sp2c-COF
shows
interesting
magnetic
properties[14d] and can be stable upon exposure to air for over one
year.[14c] Very recently, Feng et al. demonstrated that 2D CCP-
HATN can serve as an organic cathode material for lithium-ion
batteries with superb cycling stability (91% after 1000 cycles).[14b]
However, although these sp2 carbon linked COFs can be very
stable, only very few examples have been reported until now.[14]
This could be explained by the low reversibility of the formation of
C=C bonds, and the synthesis of sp2 carbon linked COFs has
been proven to be a big challenge.[14,15]
The utilizing of 2D COFs as heterogeneous photocatalyst has
attracted many attentions recently, mainly attributed to their
intrinsic properties, such as extended π-conjugated network and
aligned pore channel.[16] In principle, 2D sp2 carbon linked COF,
in which all the carbon atoms are fully conjugated, can provide an
interesting platform for heterogeneous photocatalysis. The sp2
carbon-conjugated skeletons can offer π conjugation along both
the x and y directions, which may lead to a more effective way in
transmission of π conjugation across the 2D lattice and thus
enhance the electron delocalization.[14d] In addition, the high
chemical stability can allow the framework retain during the
photocatalytic process. Unfortunately, due to the synthetic
challenges mentioned above, the application of 2D sp2 carbon-
conjugated COFs in photocatalysis have been seldom explored.
Covalent organic frameworks (COFs) represent a novel class of
crystalline porous material composed of light-weight elements
and linked by strong covalent bonds.[1] Unlike traditional polymers,
COFs are capable of precise organizing molecular species into
two- or three-dimensional (2D or 3D) networks, featuring
structural periodicity and inherent porosity. Since first reported by
Yaghi and co-workers in 2005,[2] a variety of COFs have been
announced over the past decade and found interesting
applications in molecular absorption and separation,[3] catalysis,[4]
sensing,[5] optoelectronics,[6] energy storage,[7] etc.[8] However, it
should be mentioned here, most of these reported COFs exhibited
moderate chemical stability.[1e] For example, imine-based COFs
are likely to undergo hydrolysis in acidic conditions due to the
dynamic nature of imine bond.[9] This bottleneck will greatly
hamper their practical applications, and consequently, the design
and synthesis of chemically stable COFs are highly desirable.
Over the past few years, considerable attention has been
devoted to the construction of robust COFs.[9-14] Thanks to the
effort of many groups, several types of COFs with stable linkages,
[a]
R. Chen, J-L. Shi, G. Lin, Prof. Dr. X. Lang, Prof. Dr. C. Wang
Key Laboratory of Biomedical Polymers (Ministry of Education)
College of Chemistry and Molecular Sciences,
Wuhan University, Wuhan 430072 (China)
E-mail: chengwang@whu.edu.cn
[b]
Y. Ma
Corrosion and Protection Center
University of Science and Technology Beijing
Beijing 100083, China
Supporting information for this article is given via a link at the end of
the document.
Scheme 1. Schematic Representation of the Synthesis of Por-sp2c-COF
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10.1002/anie.201902543
Angewandte Chemie International Edition
ESSAY
Herein, we report the designed synthesis and characterization
of a novel 2D porphyrin-based sp2 carbon-conjugated COF (Por-
sp2c-COF) (Scheme 1), which exhibits high chemical stability and
interesting photocatalytic properties. We choose porphyrin as the
functional molecule, as it represents a kind of highly conjugated
π-electron macrocycles with unique photophysical and redox
properties.[17] Our studies clearly show that the resulting COF
adopts an eclipsed AA stacking structure, and has a BET surface
area of 689 m2 g-1. In addition, benefiting from the nature of C=C
linkages, Por-sp2c-COF can be stable upon immersion in different
organic solvents as well as acid and base solutions. Moreover,
Por-sp2c-COF can be used as metal-free photocatalyst for the
visible-light-induced aerobic oxidation of amines to imines, with
interesting photocatalytic activity.
chemical structure of Por-sp2c-COF was then confirmed. From
the Fourier transform infrared spectrum (Figure S2), the peak at
1671 cm–1 assigned to C=O bond of the aldehyde groups nearly
disappeared, and a new peak at 2212 cm–1 belonged to cyano
groups appeared. In addition, a signal at 3027 cm–1 that should
be attributable to the C-H stretching vibration of C=CH was found,
strongly indicating the formation of C=C bond. The thermal
stability of Por-sp2c-COF was also studied by thermo gravimetric
analysis, and it is stable up to 250 °C (Figure S3).
The powder X-ray diffraction (PXRD) pattern of Por-sp2c-COF
exhibited (Figure 1a) three main peaks at 3.4°, 6.9°, 7.6°,
corresponding to the (110), (220), (310) facets, respectively. The
crystal model was then simulated using Materials Studio software
package (see Section S4 for details) and the unit cell parameters
were optimized according to density-functional tight-binding
(DFTB) calculations. The eclipsed AA stacking model (Figure 1b)
yielded a PXRD pattern (Figure 1a) in good agreement with the
experimental observed curve, whereas the staggered AB stacking
model (Figure 1c) cannot reproduce the experimental pattern
(Figure 1a). Furthermore, the Pawley refinement was performed
on the obtained powder pattern (Figure 1a), which afford a unit
cell with parameters (a = b = 36.4757 Å, c = 4.1998 Å, α = β = γ
= 90°) that are very close to those of the suggested model (a = b
= 36.5324 Å, c = 4.1892 Å, α = β = γ = 90°). The final Rwp and Rp
values converged to 2.52% and 1.95%, respectively.
Figure 1. a) PXRD pattern of observed experimental Por-sp2c-COF, Pawley
refined, difference between experimental and calculated data, calculated for
AA-stacking, and calculated for AB stacking. The inset is the enlarged PXRD
pattern of experimental and calculated for AA-stacking. Space-filling models of
the Por-sp2c-COF in b) AA and c) AB stacking modes.
Figure 2. a) SEM image of Por-sp2c-COF. b) HR-TEM image of Por-sp2c-COF.
c) N2 adsorption and desorption isotherms of Por-sp2c-COF at 77 K. The inset
is the pore size distribution of Por-sp2c-COF calculated from the quenched solid
density functional theory. d) PXRD patterns of Por-sp2c-COF measured after
treatment in boiling water, 9 M NaOH and 9 M HCl for 24 h. The PXRD of 9 M
HCl was tested after neutralization with 20% NaHCO3 aqueous solution.
In order to synthesize Por-sp2c-COF, 5,10,15,20-tetrakis(4-
benzaldehyde)porphyrin
(p-Por-CHO)[18]
and
1,4-
Scanning electron microscopy images showed that Por-sp2c-
COF has a morphology of uniform particles (Figure 2a and Figure
S7), and high-resolution transmission electron microscopy
images revealed it has a pore dimeter of ~ 1.8 nm (Figure 2b and
Figure S8). The permanent porosity of Por-sp2c-COF was
determined by measuring the nitrogen adsorption isotherm at 77
phenylenediacetonitrile (PDAN) were chosen as precursors. Due
to the low reversibility of the Knoevenagel condensation reaction,
many solvothermal conditions were carried out (Table S1 and
Figure S1). Finally, the highly crystalline Por-sp2c-COF can be
obtained by condensing p-Por-CHO and PDAN in the mixture of
o-dichlorobenzene/5 M DBU (10:1, by vol.) at 80 °C for 72 h. The
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10.1002/anie.201902543
Angewandte Chemie International Edition
ESSAY
K. As shown in Figure 2c, Por-sp2c-COF showed a typical 
sorption isotherm curve, indicating the microporous nature. The
Brunauer-Emmett-Teller surface area was calculated to be 689
m2 g–1, and the pore-size distribution analysis based on the
quenched solid density functional theory (QSDFT) model
revealed a main peak at 1.85 nm (Figure 2c). In addition, we also
studied its selective sorption of CO2 over N2 (Figure S6). By using
ideal adsorbed solution theory (IAST),[19] the adsorption selectivity
for CO2/N2 mixtures (15/85) of Por-sp2c-COF as a function of
pressure was presented, which showed a selectivity of 51 at 1 bar.
More importantly, this COF showed high chemical stability. After
immersing Por-sp2c-COF into various solvents, the COF samples
still retained the original PXRD profiles, even under harsh
conditions such as 9 M HCl and 9 M NaOH solutions (Figure 2d
and Figure S5).
The optical and electronic properties of Por-sp2c-COF were
studied. From the solid-state UV-Vis spectroscopy experiment
(Figure S12), the Soret band of the Por-sp2c-COF showed a red
shift of 32 nm compared to that of the reported imine-based Por-
COF,[20] demonstrating the C=C linkage is more effective in
transmitting π conjugation over the 2D skeleton than that of the
C=N bond.[14d] According to the absorption edge, the optical band
gap of the Por-sp2c-COF was estimated to be 1.75 eV (Figure
S13), indicating its semiconductor nature. In order to further
investigate the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) level, the cyclic
voltammetry (CV) of Por-sp2c-COF was recorded (Figure S15).
The onset reduction and oxidation potentials were -1.3 and 0.41
V, in reference to the redox potential of ferrocene/ferrocenium.
Accordingly, the HOMO/LUMO energies of Por-sp2c-COF were -
5.21 eV and -3.5 eV. In addition, the optical band gap of imine-
based Por-COF was estimated to be 1.76 eV, and the HOMO and
LUMO levels were calculated to be -5.1 eV and -3.36 eV (Figure
S17).
We then chose the transformation of dibenzylamine to N-
benzylidenebenzylamine for the systematic assessment, as the
substrate is secondary amine and the imine-based Por-COF can
be stable under the photocatalytic condition (Figure S22). As
listed in Table 1, when Por-sp2c-COF was used as photocatalyst
(entry 1), the reaction yield can reach to 99% in 30 min. It should
be pointed out that, without any special treatment or reactivation
procedure, Por-sp2c-COF was still highly active with
photocatalytic conversion yield of 97% after 5 runs (Figure S20),
and from PXRD experiment, the framework was well retained
during this recycling process (Figure S21). The factors that may
influence the photocatalytic reaction were also evaluated. From
entries 2-4, it could be concluded that photocatalyst, light and
oxygen source are all necessary for this reaction. For comparison,
the reported imine-based Por-COF (entry 5) and pyrene-based
sp2c-COF (entry 6) were also investigated as photocatalyst. The
imine-based Por-COF showed a lower conversion yield (44%),
demonstrating the fully carbon conjugated skeleton can facilitate
the electron transfer process to achieve an enhanced
photocatalytic efficiency. For the reported pyrene-based sp2c-
COF, it showed a conversion yield as low as 19%, probably due
to its relatively lower LUMO level which leads to a limited
efficiency for the activation of oxygen molecules (Figure S17).[25]
In addition, we tested the general applicability of Por-sp2c-COF as
photocatalyst. Several dibenzylamine derivatives, which are
bearing electron-withdrawing or electron-donating substituents,
were used as substrates. As shown in Table 2, in the present of
Por-sp2c-COF, all of them could be effectively converted to the
desired products with excellent conversion yield.
Table 1. Photocatalytic Oxidation of Secondary Amines to Imines by Por-sp2c-
COF[a]
Photocatalyst
Visible light, air, RT
Considering the fully conjugated structure, high chemical
stability and semiconducting behavior of Por-sp2c-COF, we
envision that it could serve as a heterogeneous metal-free
photocatalyst. We then chose the visible-light-induced aerobic
oxidation of amines to imines to test its photocatalytic activity,
Entry
Light
on
Photocatalyst
Por-sp2c-COF
Por-sp2c-COF
none
Air
+
Additive
Yield (%)[b]
1
2
3
4
5
6
7
-
99
1
off
on
+
-
since
photocatalytic
aerobic
oxidation
provides
an
+
-
none
3
environmentally friendly alternative for challenging but essential
redox chemical processes.[21] Initially, the transformation of
benzylamine to N-benzylidenebenzylamine was selected as the
model reaction. As shown in Table S3, Por-sp2c-COF exhibited
good photocatalytic performances. This result is much better than
many reported heterogeneous photocatalyst,[22] and even
comparable to some metal contained heterogeneous
photocatalyst (Table S5).[23] For example, compared with g-
C3N4,[22d] Por-sp2c-COF exhibited much better photocatalytic
performance. However, when the reported imine-based Por-COF
was used as photocatalyst under the same reaction condition
(Table S3), the COF solid was totally decomposed and no target
product was detected. This can be explained by the low chemical
stability of imine-based Por-COF, as benzylamine can react with
the imine bonds and thus destroy the framework.[24] Therefore, the
high chemical stability of the sp2 carbon-conjugated COFs can
definitely broaden their applications in various conditions.
on
Por-sp2c-COF
Por-COF[c]
-
-
on
+
-
44
19
7
on
sp2c-COF[d]
Por-sp2c-COF
+
-
on
+
Superoxide scavenger[e]
[a] Conditions: Dibenzylamine (0.1 mmol), catalyst (0.01 mmol), CH3CN (1 mL),
chlorobenzene (10 μL), irradiation with 3W white LEDs, 0.5h. [b] Conversion
determined by GC-FID with chlorobenzene as internal standard. [c] Por-COF
(0.01 mmol, 8.71 mg). [d] sp2c-COF (0.01 mmol, 8.59 mg). [e] Benzoquinone as
superoxide scavenger (1 mg).
In order to further understand the photocatalytic reaction
mechanism, we first performed spin-trapping experiment using
electron paramagnetic resonance (EPR) spectroscopy. As shown
in Figure S23, after visible-light irradiation of the air saturated
CH3CN solution containing Por-sp2c-COF and 5,5-dimethyl-1-
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10.1002/anie.201902543
Angewandte Chemie International Edition
ESSAY
sealed under vacuum and heated at 80 °C for three days. The mixture was
cooled to room temperature and the precipitate was collected by
centrifugation, washed with dichloromethane for several times, Soxhlet
extracted in tetrahydrofuran and dichloromethane for 2 days and dried
under vacuum at 80 °C for 12 h to afford modena powder (64.8 mg) in 65%
isolated yield. Elemental analysis: calculated C (84.45%), H (3.96%), N
(11.59%) and observed C (79.29%), H (4.04%), N (10.85%).
pyrroline N-oxide (DMPO), the signal for the adduct of superoxide
radical anion with DMPO was detected, indicating the formation
of the superoxide anion. In addition, when the superoxide
scavenger benzoquinone was added into the reaction system
(entry 7), the conversion yield reduced to 7% under the same
photocatalytic condition. Therefore, the key mechanistic step
should include the light-activated generation and separation of e-
-h+ pairs, followed with the reduction of oxygen with e- to
superoxide radical anion and oxidation of substrates to products
with h+, respectively.
Acknowledgements
Table 2. Photocatalytic Oxidation of Secondary Amines to Imines by Por-sp2c-
This work was financially supported by the National Natural
Science Foundation of China (21572170 and 21772149), the
Funds for Creative Research Groups of Hubei Province
(2017CFA002) and the Fundamental Research Funds for the
Central Universities.
COF[a]
Por-sp2c-COF
Visible light, air, RT
Entry
1
Substrate
Product
Time (min) Yield (%)[b]
Keywords: covalent organic frameworks • sp2 carbon-conjugated
polymers • porphyrin chemistry • metal-free photocatalyst • high
stability
30
30
30
30
30
30
99
97
97
86
91
98
2
3
4
5
6
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[a]
Conditions: Secondary amine (0.1 mmol), Por-sp2c-COF (0.01 mmol, 9.67
mg), CH3CN (1 mL), chlorobenzene (10 μL), irradiation with 3W white LEDs. [b]
Conversion determined by GC-FID with chlorobenzene as internal standard.
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In summary, we have described the designed synthesis of a
novel porphyrin-based sp2 carbon-conjugated COF. Our results
clearly showed that Por-sp2c-COF has permanent porosity and
high chemical stability, even under harsh conditions such as 9 M
HCl and 9 M NaOH solutions. Por-sp2c-COF has been used as
metal-free heterogeneous photocatalyst for the visible-light-
induced aerobic oxidation of amines to imines, and more
importantly, the inherent structure can allow Por-sp2c-COF have
several advantages as photocatalyst (e.g. reusability and high
photocatalytic performance) compared to imine-linked Por-COF.
Therefore, we believe 2D sp2 carbon linked COFs can provide an
interesting platform for developing heterogeneous photocatalytic
system. As a variety of metals can be inserted into the porphyrin
macrocycle and thus tuning their photophysical and redox
properties, the design and synthesis of 2D metalloporphyrin-
based sp2 carbon-conjugated COFs with interesting
photocatalytic properties are ongoing in our lab.
[4]
[5]
Experimental Section
Synthesis of Por-sp2c-COF: A pyrex tube was charged with p-Por-CHO
(69.72 mg, 0.096 mmol), PDAN (30 mg, 0.192 mmol), 1,2-dichlorobenzene
(4 mL) and aqueous DBU solution (0.4 mL, 5 M), the mixture was
sonicated for 5 minutes, degassed through three freeze-pump-thaw cycles,
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10.1002/anie.201902543
Angewandte Chemie International Edition
ESSAY
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10.1002/anie.201902543
Angewandte Chemie International Edition
ESSAY
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ESSAY
2D sp2 carbon-congjugated COF: A
novel 2D porphyrin-based fully sp2
carbon-conjugated COF has been
reported. Interestingly, this COF
exhibited high chemical stability under
various conditions and can be used as
Rufan Chen, Ji-Long Shi, Yuan Ma,
Guiqing Lin, Xianjun Lang and Cheng
Wang*
Page No. – Page No.
Designed
Porphyrin-Based
Conjugated
Framework
Synthesis
sp2
Covalent
for
of
a
2D
highly
efficient
metal-free
Carbon-
Organic
heterogeneous photocatalyst for the
visible-light-induced aerobic oxidation
of amines to imines.
Heterogeneous
Photocatalysis
Layout 2:
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Author(s), Corresponding Author(s)*
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Text for Table of Contents
This article is protected by copyright. All rights reserved.