Porous Organic Polymers Containing a Sulfur Skeleton for Visible Light Degradation of Organic Dyes

Article abstract of DOI:10.1002/asia.201900477

Three novel chemically stable porous organic polymers (POPs) were synthesized by the hydrothermal method; the POPs contain sulfone bonds (TpSD), no sulfur atoms (TpMD), or thioether bonds (TpTD). The catalytic mechanism of the POP with sulfone bonds was studied, and it was found that the wide visible light absorption range, high specific surface area, and the hydrophilicity of the material significantly promoted the catalytic efficiency of TpSD. The presence of O=S=O gives TpSD a higher degree of conjugation than TpMD and TpTD, so TpSD shows the strongest UV/Visible absorption and faster transmission of electrons. The photocatalytic degradation of Rhodamine B (RhB) molecules is approximately 100 % with TpSD and its pseudo-first-order rate constant is 0.0770 min^?1, which is the highest among all reported non-metallic photocatalysts. Moreover, it is also the first time that sulfur-containing polymer have been used in photocatalytic degradation of dyes.

Full text of DOI:10.1002/asia.201900477

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Porous organic polymers containing sulfur skeleton for visible
light degradation of organic dyes
Authors: Yuping Cao, Wei Liu, Jing Qian, Ting Cao, Jiemin Wang, and
wenwu Qin
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.201900477
Link to VoR: http://dx.doi.org/10.1002/asia.201900477
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201900477
Chemistry - An Asian Journal
Porous organic polymers containing sulfur skeleton for visible
light degradation of organic dyes
Yuping Cao, Wei Liu, Jing Qian, Ting Cao, Jiemin Wang, Wenwu Qin*1
Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu
Province and State Key Laboratory of Applied Organic Chemistry, College of Chemistry and
Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China
1
Corresponding author: Fax: +86-931-8912582 E-mail address: qinww@lzu.edu.cn (W. Qin)
1
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
ABSTRACT: Three novel chemically stable porous organic polymers (POPs) were
synthesized by hydrothermal method, which containing sulfone bonds (TpSD), no sulfur
atoms (TpMD) and containing thioether bonds (TpTD), respectively. We studied the
catalytic mechanism of sulfone bonds, and found that the wide visible light absorption range,
high specific surface area and the hydrophilicity of the material significantly promoted the
catalytic efficiency of TpSD. The existence of O=S=O makes TpSD have higher degree of
conjugation than TpMD and TpTD, so TpSD shows the strongest UV-visible absorption and
faster transmission of electrons. The photocatalytic degradation rate of Rhodamine B (RhB)
molecules is ~100% with TpSD and its pseudo first-order kinetic constant is 0.0770 min-1, it
is the highest among all reported non-metallic photocatalysts. Moreover, it is also the first
time that sulfur-containing polymer have been used in photocatalytic degradation of dyes.
2
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Introduction
Industrial wastewater contains high concentrations of organic dyes, and the high stability and
potential carcinogenicity of them pose a great threat to human health [1],[2], therefore, dye
degradadion is significative [3],[4]. However, industrial dye degradation today requires a lot of
energy. Solar energy as an abundant, clean, safe and sustainable energy source is considered
to be the best clean energy for dye degradation. The annual energy from the sun to the earth
is about 1.35×1024 J [5], therefore, we envisage that if visible light can be used to degrade
organic dyes, the goal of green chemistry can be achieved.
Most of the catalysts for dye degradation are metal oxides or metal sulfides (such as TiO2,
[6-8]
ZnO, CdS, etc
) with wide band gaps, which are well matched to UV light in sunlight.
However, these catalysts are easily corroded, difficultly stored, and cannot be recycled, and
more importantly, they are mainly used UV light. Thus, finding a better catalyst with higher
efficiency of visible light utilization is indispensable [9-13]. At present, many catalytic systems,
[17-22]
such as CZTS-Pt [14], NNU-36[16], CQDs/Bi2WO6 [15], etc
have been used to catalyze
some organic dyes degradation under visible light effectively. However, they can achieve
high efficiency catalysis only by the addition of cocatalysts or long-term illumination, which
greatly increases the cost of dyes degradation. What's more, these catalyst systems contain
metals, they can pose secondary pollution to the environment.
Due to their new structure and excellent properties, including low skeletal density and
3
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
toxicity, high surface area, chemistry and physics stability, superior porosity and good
performance, porous organic polymers (POPs) have been studied by more and more research
[3]
groups in recent years. Zhou and Su et al.
prepared a porous organic polymer POP-1 by
solvothermal method and used it as a catalyst to degrade RhB under visible light. When
hydrogen peroxide (H2O2) was added, the degradation efficiency in 80 min reached about
90%. When there was no H2O2 as a cocatalyst, the degradation efficiency was only 40%.
Huang et al. [23] synthesized polymer PNNs, and the degradation efficiency of the polymer to
RhB was about 90%. This work is a big breakthrough in polymer-catalyzed dye degradation.
After 5 times circulations of the catalyst, the degradation efficiency dropped to about 77%.
In addition, the dark adsorption experiment in this work indicated that the catalyst had a
strong adsorption effect on organic pollutant molecules in the dark. Thus, a large part of dye
molecules were being adsorbed instead of being degraded in the photocatalytic degradation
experiment. Verpoort et al. [24] also synthesized the polymer POP-1 by hydrothermal method,
and they studied the photocatalytic degradation of organic pollutants. This work revealed
that the degradation efficiency of POP-1 to RhB in 45 min was about 100 %, and the catalyst
also had a high catalytic efficiency of 94 % after 5 cycles. So far, POPs have made great
progress in catalyzing the degradation of dyes.
It is well known that the presence of heteroatoms such as oxygen, nitrogen and sulfur affects
the degree of conjugation and other properties of the polymer. And the degree of conjugation
4
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
affects its photocatalytic properties. However, sulfur has not been reported as a skeleton
from the current reports for dyes degradation. Therefore, we want to investigate the effect of
photocatalytic properties with sulfur atom doping in the polymer.
We synthesized three novel porous organic polymer (POPs), which containing sulfone bonds
(TpSD), no sulfur atoms (TpMD) and containing thioether bonds (TpTD), respectively
(Figure 1). The morphology, structure, thermal stability, specific surface area and pore size
of polymers were investigated by the field emission scanning electron microscopy (SEM),
fourier transform infrared spectrum (FTIR), 13C CP MAS Solid state NMR (SS-NMR),
thermogravimetric analysis and nitrogen sorption measurements. Moreover, the possibility of
visible light catalysis of polymers was analyzed by UV-vis spectroscopy. And then we
studied the degradation of RhB, Methylene blue (MB) and Rhodamine 6G (Rh6G) under
visible light without cocatalyst[25], and compared photocatalytic degradation situations of
three porous organic polymers. And then the photocatalytic efficiency of RhB under
different pH conditions and the photocatalytic degradation mechanism of RhB were studied.
The experiment results showed that TpSD has excellent photocatalytic performance for RhB,
MB and Rh6G. By modifying the POPs with O=S=O structure, the resulting TpSD polymer
retained all of the above merits while simultaneously potentiating photocatalytic efficacy.
Therefore, we get an efficient, inexpensive and nonmetallic photocatalyst to decompose dye
molecules which has the potential for industrial dye degradation.
5
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Figure 1. Schematic diagram of the synthesis of TpMD, TpTD and TpSD.
Results and Discussion
Instruments
The Fourier transform infrared spectrum (FTIR) was recorded on a Mattson Alpha-Centauri
spectrometer in the range of 4000–400 cm−1 on KBr pellet. Thermogravimetry (TG)
measurement was performed under N2 atmosphere on a Perkin-Elmer TGA-7
thermogravimetric analyzer from 32 °C to 800 °C with a heating rate of 10 °C min−1. A 300
W xenon arc lamp where a cut-off filter at 400 nm has been used to remove UV light was
used as light source for the catalytic experiments. Specific surface areas and pore volume
were calculated by using Brunauer-Emmett-Teller (BET). 13C CP MAS Solid state NMR
(SS-NMR) was taken in a Bruker 400 MHz NMR spectrometer. The UV-vis spectra for the
dyes were collected on a Cary-5000 spectrophotometer. Solid-state UV-vis spectra were
6
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
obtained by a Cary-5000 spectrophotometer. The morphologies of samples were
characterized by a field emission scanning electron microscopy (SEM) (XL30ESEM-FEG,
USA). Powder X-ray diffraction (PXRD) patterns were carried on a PANalytical BV
Empyrean diffractometer operated at 40 kV/100 mA with CuKa radiation (λ = 0.15417 nm)
at room temperature. The data were collected in the 2θ range from 3.0° to 40.0°. The average
size distribution was measured with dynamic light scattering (DLS) (BI-200SM) at room
temperature using tetrahydrofuran as the solvent.
Characterization of polymers
SEM shows that the structure of TpMD is amorphous and dynamic light scattering (DLS)
indicates that it has a large particle size with ~2700 nm (Figure 2a, b). TpTD and TpSD are
spheres with smooth surface (Figure 2c, e). DLS shows that the particle size of TpTD is
between 700 nm and 1000 nm (Figure 2d) and TpSD is between 850 nm and 880 nm, means
TpSD has more uniform particle size distribution than TpMD and TpTD. (Figure 2f).
7
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Figure 2. SEM images of (a) TpMD, (c) TpTD and (e) TpSD and DLS spectra of (b) TpMD,
(d) TpTD and (f) TpSD.
8
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
The FT-IR spectrum of TpMD (Figure S1, left) exhibits a stretching vibration band at 1618
-1
-1
-1
cm , indicating the formation of C=N. The attenuation of N-H from 3211 cm to 3446 cm
-1
and disappearance of 2885 cm (H-C=O) further confirm the formation of the C=N and the
complete reaction of monomers. Figure S1 (right) is the 13C NMR spectrum of TpMD. The
signal at ~130.5 ppm (peaks 6) can be attributed to the formation of C=N , and the other
important signals are also labeled [26]. As shown in Figure S2 (left) and S3 (left), the
-1
-1
stretching vibrations band at 1577 cm and 1610 cm represent C-S of thioether (TpTD),
-1
-1
and the stretching vibrations band at 1300 cm and 1150 cm represent the S=O
characteristic signals of sulfone (TpSD). The signals of C=N in the 13C NMR spectra of
TpTD and TpSD are varied compared with TpMD. The signal of TpTD is estimated to be
~136 ppm (Figure S2 right, peak 4), it can be attributed to the electron absorption effect of
the S atom. Similar to TpTD, the chemical shift of C=N is ~160.3 ppm (Figure S3 right, peak
1) in TpSD, because the electron absorption capacity of O=S=O group is stronger than S
atom.
The UV-vis absorption range is widened, which may be due to the formation of large
conjugated structure (Figure S4a). The broad absorption band in the region of 300-800 nm
means that POPs can be excited to produce electrons and hole (h+) under visible light,
therefore, TpMD, TpTD and TpSD can be used for visible light catalysis. As shown in
Figure S4a, it can be seen that the solid UV−vis absorption of TpSD is the strongest, because
9
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
the sulfone bond in POP makes the system more conjugate. At the same time, after replacing
the C atom (TpMD) with the S atom (TpTD), the maximum UV-vis absorption wavelength
of polymer is slightly red-shifted. In addition, the forbidden band widths of polymers were
calculated by the energy dependence formula: αhν = (hν − Eg)1/2. The forbidden bands of
TpMD, TpTD and TpSD are Eg = 1.84 eV, Eg = 2.18 eV and Eg = 2.23 eV, respectively
(Figure S4b-d). Narrower band gap width indicates clearly that lower energy can excite
electrons to produce electron-hole pairs, further to produce active species for photocatalytic
dye degradation.
The thermogravimetric analysis (TGA) was carried under N2 atmosphere. TpMD and TpTD
begin to decompose at 312.7 °C and 344.9 °C , respectively (Figure S5). As shown in Figure
S5, it exhibited that the TpSD began to decompose at 390 °C, and decomposesed less than
50 % at 800 °C. Therefore, the results show that TpMD, TpTD and TpSD all have excellent
thermal stability and offer great stability for their applications in harsh high temperature
environment. Moreover, the order of thermal stability is TpSD>TpTD>TpMD, because the
doping of sulfur element makes TpSD has a higher degree of conjugation, thereby its
polymerization is more stable. The Brunauer–Emmett–Teller (BET) surface area and pore
size were determined by nitrogen (N2) sorption measurements at 77 K. Based on nitrogen
adsorption experiment, the BET surface area of TpMD is estimated to be 112 m2/g (Figure
S6), and the maximum average pore width of TpMD is 9.6 nm (Figure S6, inset). However,
10
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
the BET surface area of TpTD is only 30 m2/g (Figure S7). As shown in Figure S10, TpSD
shows a type II isotherm, which proves that the polymer is a porous polymer and its pore size
is greater than 20 nm. The BET surface area of TpSD is 40.86 m2/g and the maximum
average pore width of TpSD is 11.8 nm (Figure S8, inset). The powder X-ray diffraction
curves of TpMD, TpTD and TpSD show that the crystallinity of TpMD is the highest (Figure
S9), proving that the structure of TpMD is more regular than TpTD and TpSD. Therefore,
the BET surface area of TpMD is the largest in three polymers. The characterization
information for the three polymers is summarized in Table 1.
Table 1. Characterization data of three different polymers
Specific Decomposition
Morphology Particle
size(nm) region(nm)[a] (ev)[b] area
(m2/g)[c]
Absorption
Eg
surface
temperature
(°C )
TpMD
TpTD
TpSD
amorphous
2700
200-700
200-700
200-750
2.34
2.21
2.45
112
312.7
344.9
390
sphere
800
30
sphere
850
40.86
[a] UV-vis absorption range.[b]Band gap.[c] The Brunauer–Emmett–Teller (BET) surface
area
Photocatalytic properties of TpSD
Both RhB and Rh6G have good stability under the visible light, and MB has low
decomposition efficiency under visible light. RhB, Rh6G and MB are typical organic dyes
pollutants in water, which are difficult to decompose under visible light. Therefore, these
11
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
pollutants were chosen as our experimental objects to evaluate the degradation efficiency of
POPs. Here, RhB was chosen as a representative to describe the photocatalytic properties of
POPs in detail. As shown in Figure 3a, the concentration of RhB does not change
significantly with visible light, it means that RhB is extremely stable under visible light.
Then the catalyst TpSD was added without visible light illuminating and found that the
change in concentration of RhB is also negligible, demonstrating that the RhB molecule is
hardly adsorbed by TpSD. However, under the visible light of xenon arc lamp, the RhB
solution added with TpSD was almost completely reacted and the degradation rate of RhB is
close to 100% in 30 min, which provides an evidence for our idea, TpSD has a superior
photocatalytic activity for RhB degradation.
To further investigate the catalytic activity of TpSD in organic pollutants under visible light,
the degradations of MB and Rh6G were investigated in the same conditions with RhB. The
degradation efficiencies of MB at 30 min and 60 min under visible light were 62.5% and
95.8% (Figure 3b) and the degradation efficiencies of Rh6G were 86.7% and 99.2% (Figure
3c), respectively. Photocatalytic experiments showed that TpSD not only has good catalytic
activity for o-diphenol organic pollutants such as RhB and Rh6G, but also has excellent
catalytic
MB.
activity
for
phenothiazine
pollutants
such
as
12
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Figure 3. Photocatalytic experiments for degradation of (a) RhB, (b) MB and (c) Rh6G over
TpSD. Photocatalytic experiment of (d) RhB, (e) MB and (f) Rh6G over TpSD, TpTD, and
TpMD.
13
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Photocatalytic experiments of TpTD and TpMD had also been researched in similar
condition. By comparing with TpSD, we find that the catalytic performances of TpTD and
TpMD were lower than TpSD (Figure 3d, e, f). This is because the presence of a sulfone
bond results in a higher degree of conjugation of TpSD, its solid UV absorption is stronger,
which is more favorable for the acceptance of photons and transfer of electrons. At the same
time, the catalytic efficiency of TpMD was higher than TpTD, it is due to the hydrophobicity
of TpTD which does not disperse well in water (Figure S10). In order to determine the
catalytic performance of TpTD, we researched the degradation of RhB dissolved in ethanol
(TpMD, TpTD and TpSD can disperse in ethanol well). The results show that the catalytic
performance of TpTD is the worst of three polymers (Figure S11), because the crystallinity
and BET specific surface area of TpTD are lower than TpMD, its structure is irregular, the
electron transport is blocked.
The dynamic tests and cyclic experiments were used to further evaluate the catalytic
degradation performance of TpSD. As shown in Figure 4a, the degradation of RhB, MB and
Rh6G followed pseudo-first-order kinetics, and the pseudo-first-order kinetics constants of
RhB, MB and Rh6G were 0.0770 min-1, 0.0308 min-1 and 0.0221 min-1 (Figure 4b),
respectively. The degradation of RhB by TpSD was studied under different pH conditions
(Figure 4c). It was found the high pH could lead to the low degradation efficiency, and when
pH  7, the degradation efficiency was reduced to 50%. It can be attributed to the fact that
14
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
H+ combines with nitrogen atoms on the imine bond can form an ammonium salt, which
accelerates electron transport. Therefore ， the stronger the acidity, the higher catalytic
efficiency of TpSD.
In order to compare the catalytic performance of TpSD with the classical metal oxide
photocatalyst under visible light, we also carried out the catalytic experiments of RhB, MB
and Rh6G under the same conditions using commercial TiO2 (Figure S12). The experimental
results confirmed that TpSD has more excellent photocatalytic properties than metal oxides.
The degradation of organic pollutants by other photocatalysts is shown in Table S1.
Compared with non-metallic photocatalysts, TpSD has the highest pseudo-first-order kinetics
constant of RhB in all currently reported photocatalysts. Compared to metal-containing
photocatalysts, TpSD is non-toxic and has higher catalytic efficiency without the addition of
any cocatalyst (Table S1).
15
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Figure 4. (a) Pseudo-first-order kinetics curves of the photocatalytic degradation of RhB,
MB and Rh6G; (b) The pseudo-first-order kinetics constants for the degradation of RhB, MB
and Rh6G; (c) Degradation of RhB under different pH conditions; (d) Visible-light driven
photocatalytic degradation of RhB with different scavengers or without O2 over TpSD.
The reaction mechanism was explored by adding scavengers. As shown in Figure 4d, when
EDTA-2Na and isopropanol (IPA) were added as scavenger for hole (h+) and hydroxyl
16
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
radical (•OH), respectively. We found that the photocatalytic efficiency was lower when
EDTA-2Na was added, meanwhile, there was almost no change when IPA was added. It
manifests that the RhB molecule could be oxidized by h+ produced during the reaction, but
the oxidize effect of •OH is very weak. The dissolved oxygen in the water was removed by
•-
three freeze-pump-thaw cycles so that the superoxide anion radicals (O2 ) could not be
produced in the reaction system. After 30 min, the catalytic efficiency dropped to 10.7%.
Therefore, the mechanism of TpSD photocatalytic degradation of RhB are summarized as
equations (1) – (4) [27, 28]
:
As see in Figure 4d, the Eq (3) and Eq (4) are main reactions in the photocatalytic reaction.
The cycle experiments of RhB degradation under visible light were performed to estimate
the photostability of TpSD (Figure S13). TpSD showed almost no loss of photocatalytic
activity after five cycle experiments. By comparing with the data of UV-vis, FT-IR, SEM
and PXRD before and after the catalysis, it was found that TpSD was stable during the
photocatalytic reaction (Figure S14-17), it is due to a high degree of conjugation, which can
lead to a more stable structure.
17
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Conclusions
In summary, we synthesized three novel porous organic polymers and studied their
photocatalytic properties. The highest conjugated O=S=O structure of TpSD gives it a broad
UV-vis absorption range (200-800 nm) and strong absorbance, indicating that TpSD has
possibility in photocatalytic. Compared with other non-metallic materials, the catalytic
performance (k =0.0771 min-1) of TpSD was the most excellent of all the reports. Under the
same conditions, TpSD has more excellent catalytic performance than commercial catalyst
TiO2. Due to its narrow band gap, TpSD is beneficial to the absorption of visible light, and
the insolubility in water of TpSD means it cannot cause secondary pollution. Therefore,
TpSD is a new, safety, and environmentally-friendly material for solving water pollution,
and may replace metals containing photocatalyst in the future.
Experimental Section
All reagents are analytical grade. 4, 4'-diaminodiphenylsulfone (C12H12N2O2S), 4, 4'-
thiodianiline (C12H12N2S), 4,4'-methylenedianiline (C13H14N2), phloroglucinol (C6H6O3),
hexamethylenetetramine (C6H12N4), trifluoroacetic acid (CF3COOH, 99.5%), concentrated
hydrochloric acid (HCl, 38%), mesitylene (C9H12, 99%), 1,4-dioxane (C4H8O2, 99.5%) and
glacial acetic acid (C2H4O2, 36%) were purchased from the supplier except 2,4,6-
triformylphloroglucinol (Synthesis process details in Supporting Information).
Preparation of TpMD
18
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
4, 4'-methylenedianiline (27.90 mg, 0.15 mmol) was dissolved in 1, 4-dioxane (1.5 mL), and
added the mixture to a 10 ml glass bottle with 2, 4, 6-triformylphloroglucinol (21.00 mg, 0.10
mmol) and 1, 4-dioxane (1.5 mL). Added 3 M acetic acid (0.4 mL) in the bottle, and allowed
it to stand at room temperature for three days. The resulting product was washed several
times with tetrahydrofuran, acetone and dichloromethane, respectively. The product was
dried under vacuum at 60 °C to give a yellow powder. Anal. Calcd (%) For C21H18N2O3: C,
72.83; H, 5.20; N, 8.09; found: C, 74.72; H, 5.42; N, 8.19.
Preparation of TpTD
2, 4, 6-triformylphloroglucinol (21.00 mg, 0.10 mmol) and 4, 4'-thiodianiline (32.00 mg,
0.15 mmol) were added to 10 mL reaction flask, 1.5 mL dioxane and 1.5 mL mesitylene
were added subsequently. After ultrasounding for 1 minute, 0.4 mL of a 3 M acetic acid
solution was added. The reaction flask was sealed and heated to 120 °C for 2 days. The
resulting product was washed several times with tetrahydrofuran, acetone and
dichloromethane, respectively. The product was dried under vacuum at 60 °C to give a
yellow powder. Anal. Calcd (%) For C20H16N2O3S1: C, 65.93; H, 4.40; N, 7.69; found: C,
64.25; H, 3.89; N, 7.92.
Preparation of TpSD
In the similar way to the preparation of TpTD. 2, 4, 6-Triformylphloroglucinol (21.00 mg,
0.10 mmol), 4, 4'-diaminodiphenylsulfone (37.20 mg, 0.15 mmol), 1.5 mL dioxane and 1.5
19
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
mL mesitylene and 0.4 mL 3 M acetic acid solution were added in 10 mL reaction flask. The
reaction flask was sealed and heated to 120 °C for 2 days. The resulting product was washed
several times with tetrahydrofuran, acetone and dichloromethane. The product was dried
under vacuum at 60 °C to give a yellow powder. Anal. Calcd (%) For C20H16N2O5S1: C,
60.61; H, 4.04; N, 7.07; found: C, 58.24; H, 3.64; N, 7.11.
20
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
Acknowledgements
The authors would like to thank the Natural Science Foundation of China (no. 21771092).
Conflict of interest
The authors declare no conflict of interest.
Keywords: sulfur atom doping, porous organic polymers, visible light, photocatalytic,
recyclable
[1] D. Chatterjee, S. Dasgupta, Journal of Photochemistry and Photobiology C: Photochemistry Reviews.
2005 ,6, 186-205.
[2] L.R. Aveiro, A.G.M. Da Silva, E.G. Candido, V.S. Antonin, L.S. Parreira, R. Papai, I. Gaubeur, F.L. Silva,
M.R.V. Lanza, P.H.C. Camargo, M.C. Santos, Chemosphere.2018, 208, 131-138.
[3] P. Liu, L. Xing, H. Lin, H. Wang, Z. Zhou, Z. Su, Science Bulletin. 2017, 62, 931-937.
[4] L. Cai, Y. Li, Y. Li, H. Wang, Y. Yu, Y. Liu, Q. Duan, Journal of Hazardous Materials.2018, 348, 47-55.
[5] C. Chen, W. Ma, J. Zhao, Chemical Society Reviews. 2010, 39, 4206-4219.
[6] L.-L. Shi, T.-R. Zheng, L.-M. Zhu, K. Li, B.-L. Li, B. Wu, Inorganic Chemistry Communications. 2017, 85,
16-20.
[7] C. Liu, J. Chen, H. Che, K. Huang, P.A. Charpentier, W.Z. Xu, W. Shi, H. Dong, RSC Advances. 2017, 7,
8429-8442.
[8] H. Kazuhito, I. Hiroshi, F. Akira, Japanese Journal of Applied Physics. 2005, 44, 8269.
[9] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science. 2001, 293, 269.
[10] S.U.M. Khan, M. Al-Shahry, W.B. Ingler, Science. 2002, 297, 2243.
[11] Angewandte Chemie, 2003, 115, 1059-1062.
[12] Z. Zou, J. Ye, K. Sayama, H. Arakawa, Nature. 2001, 414, 625.
[13] H. Murayama, K.-i. Shimizu, N. Tsukada, A. Shimada, T. Kodama, Y. Kitayama, Chemical
Communications. 2002, 0, 2678-2679.
[14] A.S. Xuelian Yu , Xiaoqiang An, Zhishan Luo, Maria Ibanez , and Andreu Cabot, J. Am. Chem. Soc. 2014,
́
̃
136, 9236-9239.
[15] Q.X. Hongmei Zhao, Hongzhu Xing, Dashu Chen, and Hong Wang, ACS Sustainable Chem. Eng. 2017, 5,
4449-4456.
[16] J.X. Jun Di, Yuping Ge, Hongping Li, Haiyan Ji, Hui Xu, Qi Zhang,, M.L. Huaming Li, Applied Catalysis
B: Environmental. 2014, 168-169, 51-56.
[17] C.A. Zhang, L. Jiang, J., J.Mater. Chem. A. 2015, 3, 3074-3081.
[18] C.-F.Q. Zhang, L.-G.; Ke, F.; Zhu, Y.-J.; Yuan, Y.-P.; Xu, G.-, X. S.; Jiang, J. Mater. Chem. A. 2013, 1,
21
This article is protected by copyright. All rights reserved.

10.1002/asia.201900477
Chemistry - An Asian Journal
14329-14334.
[19] X.Z. Zhu, S.; Peng, Y.-F.; Li, B.-L.; Wu, B., CrystEngComm. 2013, 15, 9154−9160.
[20] H. Wang, X. Yuan, Y. Wu, G. Zeng, X. Chen, L. Leng, Z. Wu, L. Jiang, H. Li, Journal of Hazardous
Materials. 2015, 286, 187-194.
[21] N.M. Mahmoodi, J. Abdi, M. Oveisi, M. Alinia Asli, M. Materials Research Bulletin. 2018, 100, 357-366.
[22] W.-X.N. Kun Fan, Lu-Ping Wang, Chwen-Haw Liao, Song-Song Bao, and Li-Min Zheng, Chem. Eur. J.
2017, 23, 6615 – 6624.
[23] X.-H.H. Lei Zhang, Jin-Song Hu, Jian Song, and Il Kim, Langmuir. 2017, 33, 1867-1871.
[24] J.C. Ipsita Nath, Philippe M. Heynderickx, Francis Verpoort, Applied Catalysis B: Environmental. 2018,
227, 102–113.
[25] A.S. Namrata Saha, Abhisek Brata Ghosh, Papri Mondal, Jit Satra, Bibhutosh Adhikary, Ecotoxicology
and Environmental Safety. 2018, 160, 290–300.
[26] Y.C. Wei Liu, Wenzhuang Wang, Deyan Gong, Ting Cao, Jing Qian, W.Q.a.H.G. Kanwal Iqbal, Chem.
Commun. 2019, 55, 167-170 .
[27] M.-K.W. Shuai-Ru Zhu, Wen-Na Zhao, Peng-Fei Liu, Fei-Yan Yi, Guo-Chang Li, Kai Tao, and Lei Han,
Cryst. Growth Des. 2017, 17, 2309-2313.
[28] W.A. Liu, Z.; Zhang, L., J. Hazard. Mater. 2012, 257-264.
22
This article is protected by copyright. All rights reserved.