A Triazine-Based Analogue of Graphyne: Scalable Synthesis and Applications in Photocatalytic Dye Degradation and Bacterial Inactivation

Article abstract of DOI:10.1002/chem.201905133

Graphyne, a theorized carbon allotrope possessing only sp- and sp²-hybridized carbon atoms, holds great potentials in many fields, especially in catalysis and energy-transfer/storage devices. Using a bottom-up strategy, we synthesized a new N-doped graphyne analogue, triazine- and 1,4-diethynylbenzene-based graphyne TA-BGY, in solution in gram-scale. The unique sp/sp² carbon-conjugated TA-BGY possesses an extended porous network structure with a BET surface area of approximately 300 m² g^?1. Owing to its low optical band gap (1.44 eV), TA-BGY was expected to have many applications, which were exemplified by the photodegradation of methyl orange and photocatalytic bacterial inactivation.

Full text of DOI:10.1002/chem.201905133

A Journal of
Accepted Article
Title: A Novel Triazine-Based Analog of Graphyne: Scalable Synthesis
and Applications in Photocatalytic Dye Degradation and Bacterial
Inactivation
Authors: Tao Chen, Wen-Qian Li, Xiao-Jia Chen, Yun-Zhe Guo, Wei-
Bo Hu, Wen-Jing Hu, Yahu A. Liu, Hui Yang, and Ke Wen
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. Eur. J. 10.1002/chem.201905133
Link to VoR: http://dx.doi.org/10.1002/chem.201905133
Supported by

10.1002/chem.201905133
Chemistry - A European Journal
DOI: 10.1002/ ((please add manuscript number))
Article type: (Full Paper)
A Novel Triazine-Based Analog of Graphyne: Scalable Synthesis and Applications in
Photocatalytic Dye Degradation and Bacterial Inactivation
Tao Chena,b, Wen-Qian Lia,b, Xiao-Jia Chena, Yun-Zhe Guoa,b, Wei-Bo Hu*a, Wen-Jing Hua,
Yahu A. Liuc, Hui Yang*a,d and Ke Wen*a,d
a Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, P.
R. China.
E-mail: huwb@sari.ac.cn; yangh@sari.ac.cn; wenk@sari.ac.cn
b University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
c Medicinal Chemistry, ChemBridge Research Laboratories, San Diego, CA 92127, USA
d School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, P.
R. China
Keywords: graphyne analog, aromatic nucleophilic substitution reaction, hydroxyl radical,
photocatalytic dye degradation, antibiosis
Graphyne, a theorized carbon allotrope possessing only sp- and sp2-hybridized carbon atoms,
holds great potentials in many fields, especially in catalysis, energy transfer/storage devices.
Using a bottom-up strategy, we synthesized a new N-doped graphyne analog, triazine- and
1,4-diethynylbenzene-based graphyne TA-BGY, in solution in gram-scale. The unique sp/sp2
carbon-conjugated TA-BGY possesses an extended porous network structure with a BET
surface area of ca. 300 m2g-1. Owing to its low optical band gap (1.44 eV), TA-BGY was
expected to have many applications which were exemplified by the photodegradation of
methyl orange and photocatalytic bacterial inactivation.
1
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
1. Introduction
Graphyne (GY), a theorized one-atom thick carbon allotrope consist of sp2 hybridized carbons
(benzene rings) bridged by ethylenic groups (sp carbons), is expected to possess two-
dimensional π-conjugated networks, uniformly distributed pores and unique mechanical and
electronic properties.[1] Different from graphene which does not have an electronic bandgap
because the valence and conduction bands are slightly overlapped, GY is predicted to be a
natural semiconductor with intrinsic band gap (0.5 - 0.6 eV) owing to the special acetylenic
−C≡C− bridges between the benzene rings.[2] Therefore, GY and its analogs are considered
to be potentially useful in various fields owing to their unique band gap properties.[3] So far,
the true GY, in which only one acetylenic bond between adjacent benzene rings, has not been
created due to the synthetic challenge, thus, it has only been studied through various
computational simulations, and the exact properties of this theoretical material remains
unknown. Despite the unsuccessfulness in the synthesis of true graphyne, some analogous
structures of GY have been created during the past years.[4] For example, graphdiyne (GDY),
in which its benzene rings are connected by diacetylenic bonds, was synthesized on the
surface of copper via a cross-coupling reaction by Li’s group in 2010.[4a] Ever since, several
synthetic methods of GDY have been developed, and various applications of this new
material have been explored (Figure 1).[5] In 2017, Li, Xiao and co-workers described a
preparation of a carbon-rich network whose structure was close to hydrogen substituted
graphyne (H-GY) through alkyne metathesis polymerization (Figure 1).[4b] Very recently,
Yang, Huang and co-worked reported the synthesis of three graphyne analogs, hydrogen
substituted graphyne (H-GY), methyl substituted graphyne (Me-GY) and fluorine substituted
graphyne (F-GY) at a liquid/liquid interface (Figure 1).[4f] Nonetheless, the true GY material
2
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
is yet to be made. On the other hand, “more synthetically approachable” heteroatom-doped
GY, especially N-doped GY, could hold similar importance in designing GY analogs
potentially useful in photocatalysis and electronics as introducing heteroatoms is an efficient
and essential method to adjust the band gaps and electronic structures of carbon materials.[6]
Nitrogen-doping of carbon-based materials is usually implemented though three different
strategies, such as chemical vapor deposition, pyrolysis of N-rich precursors, and post heating
with N-containing substances. However, these approaches suffer drawbacks, such as varieties
of species of N-containing substructures, randomness of the positions of N atoms as well as
uncontrolled N percentage. Therefore, homogeneous 2D carbon materials have to be
synthesized through a strategy which ensures N atoms to be in specific type and at specific
locations in controllable percentage. One example was the bottom-up synthesis of triazine-
graphdiyne (TA-GDY) reported by Hou, Huang and co-workers in 2018 (Figure 1).[4g] Herein,
we report a gram-scale synthesis of triazine and 1,4-diethynylbenzene-based analog of
graphyne (TA-BGY) through a bottom-up strategy in which C-C bonds were formed through
aromatic nucleophilic substitution reactions (SNAr) of cyanuric chloride with 1,4-
diethynyllithium benzene. TA-BGY was found to possess a low optical band gap of 1.44 eV,
and demonstrated high efficiency in photodegradation of methyl orange (99%) and
photocatalytic bacterial inactivation (no detectable bacteria after 1 h irradiation).
3
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
Figure 1. Graphyne and its analogs: Graphyne (GY), graphdiyne (GDY), triazine-graphdiyne
(TA-GDY), hydrogen-substituted graphyne (H-GY), fluorine-substituted graphyne (F-GY),
methyl-substituted graphyne (Me-GY), and triazine- and 1,4-diethynylbenzene-based
graphyne (TA-BGY, this work). Gray, carbon (C); blue; nitrogen (N); green, fluorine(F).
2. Results and Discussion
Our group previously reported a method to synthesize covalent triazine networks (CTNs)
through aromatic nucleophilic substitution reaction of cyanuric chloride and para-
dilithiumaromatic reagents under mild conditions.[7] We designed a triazine and 1,4-
diethynylbenzene-based analog of graphyne (TA-BGY) which, we envisioned, could be
4
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
synthesized by using the similar strategy - aromatic nucleophilic substitution reaction of
cyanuric chloride and 1,4-diethynyllithium benzene (SNAr). In light of this idea, a model
reaction of cyanuric chloride and phenylethynyl lithium was carried out, and the resulting
product 2,4,6-tris(phenylethynyl)-1,3,5-triazine was confirmed by NMR spectroscopy and
mass spectrometry (Supporting Information). Under very similar reaction conditions used in
the optimized model reaction, TA-BGY was successfully synthesized through the reaction of
cyanuric chloride and 1,4-diethynyllithium benzene in a yield of 75% (Scheme 1, and
Supporting Information). The as-synthesized TA-BGY was characterized by solid-state 13C
cross polarization magic angle spinning nuclear magnetic resonance spectroscopy (13C
CP/MAS NMR), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible diffuse
reflectance spectroscopy (UV-Vis DRS), X-ray photoelectron spectroscopy (XPS),
thermogravimetric analysis (TG), powder X-ray diffraction analysis (PXRD), field emission
scanning electron microscopy (FE-SEM), field emission transmission electron microscopy
(FE-TEM, TEM-Mapping) and atomic force microscopy (AFM).
Scheme 1. Synthesis of TA-BGY
5
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
The solid-state 13C-NMR spectrum of TA-BGY showed the presence of sp-hybridized carbon
of the triple bond (~ 80 ppm) and sp2-hybridized carbon of the benzene unit (120 - 150 ppm)
and the triazine unit (~ 170 ppm), similar to the reference compound [2,4,6-
tris(phenylethynyl)-1,3,5-triazine] which showed corresponding signals at 80-100 ppm, 120-
150 ppm, and 160-170 ppm, respectively (Figure 2A and Figure S5, Supporting
Information).[8] In the Fourier transform infrared (FTIR) spectrum (Figure 2B-2C), the
disappearance of characteristic carbon-chloro bond of cyanuric chloride at 850 cm-1 as well as
terminal ethynyl carbon-proton stretch vibration of 1,4-dithynylbenzene at 3277 cm-1 of the
starting materials, together with the appearance of vibrational band of triazine unit at 1510
cm-1 (carbon-nitrogen stretching), benzene unit at 1360 cm-1 (benzene ring breathing), and
carbon-carbon triple bond unit at 836 cm-1 and ca. 2200 cm-1 (carbon-carbon triple bond
stretching), implied the formation of TA-BGY.[8-9] In the XPS spectrum of the TA-BGY
(Figure 3), the emergence of the peaks with binding energies of 398.8 eV (N 1s of the triazine
ring), 284.3 eV (C 1s of benzene unit), 285.2 eV (C 1s of ethynyl unit) and 286.8 eV (C1s of
triazine ring) provided additional evidence of the formation of TA-BGY. Meanwhile, the
ratio of Ctriazine:Cphenyl:Cethynyl in the XPS spectrum of TA-BGY was 1:3.1:1.7, which was close
to its theoretical value of 1:3:2 (an infinitely extended two-dimensional TA-BGY plane).[8]
Scarcely any chloride peaks were found either in the survey spectrum or in Cl 2p scan (Table
S1, Supporting Information), indicating a complete substitution of chloro atoms in cyanuric
chloride by the 1,4-diethynylbenzene function.[7] The O 1s peaks found in the XPS spectrum
could come from physically adsorbed oxygen or water molecules, which are typical for most
carbon-based materials.[10] All of the data listed above confirmed the formation of TA-BGY
unambiguously. In addition, TG analysis indicated that TA-BGY started decomposition at ~
300 ºC and experienced ~ 60% weight loss at 1000 ºC in nitrogen atmosphere (Figure 2D).
6
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
The weight loss around 100 ℃ could probably be attributed to the loss of physically adsorbed
solvent and water molecules.
Figure 2. (A) Solid-state 13C CP/MAS NMR spectrum of TA-BGY; (B) and (C) FTIR spectra
of TA-BGY and its reaction precursors 2,4,6-trichloro-1,3,5-triazine and 1,4-
diethynylbenzene; (D) TG analysis of TA-BGY.
Morphological details of TA-BGY were studied by field emission scanning electron
microscope (FE-SEM), field emission transmission electron microscopy (FE-TEM), and
atomic force microscopy (AFM). FE-TEM and FE-SEM images of TA-BGY showed
extended porous network structures with branched morphologies (Figure 4A-4C). TEM-
Mapping of TA-BGY indicated carbons and nitrogens were evenly distributed in the
materials (Figure S1, Supporting Information). The FE-SEM and FE-TEM images of TA-
7
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
BGY also revealed its layered or stacked structures, which was confirmed by the observation
of lamellar structures in its AFM images (Figure 4D, samples for AFM were prepared by
sonication of TA-BGY in ethanol at a concentration of 0.1 mg/mL). The thickness of 3.4 nm
with a lateral micrometre scale in AFM image indicated that the nano-sheets of TA-BGY
were composed of less than 10 one-atom-thick layers (Figure 4D-4E).[11]
Figure 3. X-ray photoelectron spectroscopy of TA-BGY: (A) survey spectra; (B) N 1s scan;
(C) C 1s scan.
8
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
Figure 4. FE-TEM images of TA-BGY: (A) 200 nm scale; (B) 20 nm scale; (C) FE-SEM
image of TA-BGY; (D) Atomic force microscopy topography of TA-BGY; (E) Height profile
of the TA-BGY layers shown in D.
The porous property of TA-BGY was evaluated by nitrogen adsorption-desorption
measurement at 77K (Figure 5A-5B), and a characteristic type IV adsorption isotherm was
obtained, typical for materials with mesoporous porosity.[12] The Brunauer-Emmett-Teller
9
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
(BET) surface area of TA-BGY was ca. 300 m2g-1, and a broad pore diameter distribution (1.2
nm, 17 nm and 30~160 nm) was found by DFT method. The pore with a width of 1.2 nm is
possibly attributed to hexagon pores formed from eclipsed stacking layers of TA-BGY
(Figure S20, Supporting Information). Powder X-ray diffraction (PXRD) measurement of
the TA-BGY showed no distinct sharp peaks, declaring its amorphous nature. The lack of
long-range order for TA-BGY implied that its pore structures could be formed from its
unordered curling and stacking.
Figure 5. (A) Nitrogen sorption isotherm of TA-BGY; (B) Pore size distributions of TA-
BGY; (C) PXRD pattern of TA-BGY; (D) UV-Vis DRS spectrum of TA-BGY (insert:
Kubelka-Munk transformed reflectance spectrum of TA-BGY).
10
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
DFT calculation indicated that TA-BGY possesses an optical band gap of 1.44 eV with a -
5.94 eV (vs. vacuum) valence band, and a -4.50 eV (vs. vacuum) conduction band (Support
information). In addition, the theoretical optical band gap of TA-BGY obtained by DFT
calculation (1.44 eV) is pretty close to the experimental one (1.44 eV), extrapolated from TA-
BGY’s Kubel-Munk transformed reflected spectrum (Figure 5D, insert),[13] the mathematical
equivalent transformation of UV-Vis DRS (Figure 5D). The optical band gap of TA-BGY
(1,4-diethynylphenyl linkage) is narrower than that of CTF-1 (2.69 eV, phenyl linkages) and
CTF-2 (2.56 eV, biphenyl linkages), but broader than that of GDY (0.5-0.6 eV).[2b] Such a
narrow band gap for TA-BGY implies its better electrical conductivity, and easier generation
of electron/hole pairs under excitation of external energy.[14] The UV-Vis diffuse reflectance
spectrum (UV-Vis-DRS, Figure 5D) of the dark-brown TA-BGY showed a broad intrinsic
absorption (ranged in ultraviolet, visible light and infrared), which could be attributed to the
π-π* electron transition of Csp2 and Nsp2 in the polymeric networks.[9] Such a broad light
absorption for TA-BGY unveiled its potential of being used in photocatalysis, such as in
photocatalytic dye degradation and bacterial inactivation.[15]
Graphene does not have an electronic bandgap, but GY is expected to be a natural
semiconductor with intrinsic band gap (predicted 0.5 - 0.6 eV) owing to the special acetylenic
−C≡C− bridges between the benzene rings.[2] With an even wider band gap (1.44 eV), TA-
BGY, as a N-doped analog of GY, was projected to be a good photocatalyst. Electron spin
resonance (ESR) was employed to detect the generation of hydroxyl radicals in an aqueous
solution containing TA-BGY under light irradiation with 5,5-dimethyl-1-pyrroline N-oxide
•
(DMPO) as a trapping agent for OH (Figure 6A). As expected, a clear four-line spectrum
with peaks intensity ratio of 1:2:2:1 (g=2.001, aH = aN = 1.50 mT) was observed under the
11
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
irradiation of simulated sunlight (AM 1.5G), and the intensity of the corresponding signal of
•
DMPO- OH adduct increased along with the irradiation time, confirming the generation of
hydroxyl radicals by TA-BGY under sunlight irradiation.[16] It has been well reported that
hydroxyl radical possesses can break down dye compounds.[17] Subsequently, the oxidative
ability of TA-BGY as a photocatalyst was examined through photodegradation of an azo dye
- methyl orange (MO), which was widely used in industries of textile, leather, food and
cosmetics, and therefore frequently found in waste water.[18] Using a Xe 500W lamp with an
AM 1.5G cut-off filter as a light source, the decomposition of MO in water (30 mg/L)
containing dispersed TA-BGY (2 mg/mL) was monitored. As shown in Figure 6B, MO is
hardly degraded by light irradiation without a photocatalyst (blue curve), and slight decrease
of MO concentration in the TA-BGY dispersed solution before irradiation could be attributed
to the physical absorption of MO by the porous TA-BGY (black curve). After a 8 h of
irradiation (125 mW/cm2), ca. 80% of MO was degraded (red curve). By increasing the power
density of the irradiation light to 150 mW/cm2, 99% of MO was found to be degraded within
8 h (Figure 6C). This photocatalyst was found to be stable under light irradiation as evidenced
by its repeated use in MO degradation without significant loss of its photocatalytic activity
(Figure 6C), albeit the slight gradual decrease of photocatalytic activity possibly caused by its
loss in recovery after every recycling.
Theoretically, the Highest Occupied Molecular Orbital (HOMO), the second highest HOMO
(HOMO-1) and the Lowest Unoccupied Molecular Orbital (LUMO) of MO predicted at the
DFT-B3LYP/6-31G level of theory are -2.6350 eV, -3.201 eV and 0.0158 eV (vs. vacuum),
respectively.[19] Obviously, the energy level of MO’s HOMO, or even HOMO-1, is higher
than conduction band edge of TA-BGY, indicating photosensitization of MO is obstructed
12
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
(Figure S18, Supporting Information).[20] Therefore, we concluded that the degradation of
MO did not resulted from photosensitizer-assisted photocatalytic degradation.
Figure 6. (A) Electron spin resonance (ESR) spectra of TA-BGY in the dark, and under the
light irradiation for 60s and 600s in an aqueous solution containing DMPO as a trapping agent
•
for OH; (B) Photodegradation of MO irradiated under simulated sunlight (AM 1.5G, 125
mW/cm2); (C) Degradation rate of MO catalyzed by TA-BGY during the first 5 cycles; (D)
The filtrate of a solution of MO and TA-BGY after 8 h of simulated sunlight irradiation (AM
1.5G, 150 mW/cm2) (b), an aqueous solution of MO (c) (3 mg/mL); and ultrapure water (a).
Water pollution is one of the most serious ecological threats today.[21] The ingestion of
bacteria though drinking polluted water may lead sepsis and generalized infection.[22] Sunlight
has been used for water disinfection via direct or indirect mechanisms. Direct mechanisms
involve ultraviolet light to interact directly with essential biomacromolecule (protein, nucleic
13
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
acid, deoxyribonucleic acid etc.) in the microorganisms to cause inactivation.[15b, 23] Since
ultraviolet part takes only 4% of the sunlight in terms of energy, disinfection of water through
direct mechanisms is not efficient.[24] Indirect mechanisms involve photons that interact with
chromophores either within the organism or external to the organism to create reactive oxygen
species (ROS) that subsequently cause microorganism inactivation. Thus, developing new
materials that can efficiently utilize visible light for water disinfection through indirect
mechanisms is highly desirable. Given that highly active hydroxyl radicals could be generated
by TA-BGY under simulated sunlight irradiation, we envisioned that TA-BGY could be used
in disinfection of water, and had its photocatalytical antimicrobial activity evaluated
(Supporting Information). The disinfection experiment was performed with using a aqueous
suspension of Escheichia coli (E. coli) under irradiation of simulated sunlight with power
density of 100 mW/cm2. TA-BGY and the irradiation of simulated sunlight were used as
variables in the controlled experiment, and bacteria were measured by colony forming units
(CFU/mL) (Figure 7A). Hardly any inactivation of E. coli was observed in the suspension in
the presence of TA-BGY in the dark (black curve) or the one under the simulated irradiation
without TA-BGY (red curve), but, in the suspension of E. coli in the presence of TA-BGY
under irradiation, the numbers of live bacteria decreased sharply after 45 min, and showed a
thorough elimination of live E. coli after 60 min (blue curve in Figure 7A and Figure S21,
Supporting information), together with the incompleteness of the cell morphology (Figure
7B - 7C and Supporting Information). The free radicals in intracellular/extracellular
locations of the bacterial cell and damaged the cell membrane and in turn the proteins, DNA
and intracellular systems by increase the oxidative stress in the cell,[25] demonstrating strong
photocatalytic disinfection activity of TA-BGY toward E. coli.
14
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
Figure 7. (A) Disinfection performance of TA-BGY (data were obtained five independent
experiments, and the red circle mean no detectable level of bacteria (E. coli); Transmission
Electron micrographs of E. coli treated with TA-BGY in the dark (B) and under the light (C).
3. Conclusion
In summary, we have developed a bottom-up strategy to synthesize a N-doped graphyne
analog, triazine- and 1,4-diethynylbenzene-based graphyne (TA-BGY), in gram-scale through
aromatic nucleophilic substitution reactions (SNAr) of cyanuric chloride with 1,4-
diethynyllithium benzene. The as-synthesized TA-BGY was found to possess an extended 2D
porous network structure with a BET surface area of ca. 300 m2g-1 and a narrow optical band
15
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
gap of 1.44 eV. The abilities of TA-BGY in photocatalytic dye degradation and antimicrobial
disinfection have unveiled its potentials in photocatalytic water purification. The study on the
design and synthesis of other novel hetero-doped graphyne analogs is underway in our
laboratory.
Supporting Information
Supporting Information is available from the Wiley Online Library or from the author.
Acknowledgments
This research was financially supported by the National Key Research program
(2017YFA0206500), the Science and Technology Commission of Shanghai Municipality
(16DZ1100300, 18DZ1100403), and the National Natural Science Foundation of China
(21871281). We thank Dr. Gang Chen from Donghua University for his assistance in
morphology tests and NMR Core Facility from School of Life Science and Technology at
ShanghaiTech University for acquisition of the solid-state 13C CP/MAS NMR spectra.
Conflict of interest
The authors declare no conflict of interest.
Received: ((will be filled in by the editorial staff))
Revised: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))
16
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
References
[1]
[2]
[3]
a) R. H. Baughman, H. Eckhardt, M. Kertesz, J. Chem. Phys. 1987, 87, 6687; b) A.
Hirsch, Nat. Mater. 2010, 9, 868; c) C. S. Huang, Y. J. Li, N. Wang, Y. R. Xue, Z. C.
Zuo, H. B. Liu, Y. L. Li, Chem. Rev. 2018, 118, 7744.
a) Q. Tang, Z. Zhou, Z. F. Chen, Nanoscale 2013, 5, 4541; b) N. Narita, S. Nagai, S.
Suzuki, K. Nakao, Phys. Rev. B 1998, 58, 11009; c) W. B. Wan, S. C. Brand, J. J. Pak,
M. M. Haley, Chemistry – A European Journal 2000, 6, 2044.
a) X. Gao, H. B. Liu, D. Wang, J. Zhang, Chem. Soc. Rev. 2019, 48, 908; b) N. Wang,
J. He, Z. Tu, Z. Yang, F. Zhao, X. Li, C. Huang, K. Wang, T. Jiu, Y. Yi, Y. Li, Angew.
Chem. Int. Ed. 2017, 56, 10740; c) S. Wang, L. X. Yi, J. E. Halpert, X. Y. Lai, Y. Y.
Liu, H. B. Cao, R. B. Yu, D. Wang, Y. L. Li, Small 2012, 8, 265; d) N. L. Yang, Y. Y.
Liu, H. Wen, Z. Y. Tang, H. J. Zhao, Y. L. Li, D. Wang, Acs Nano 2013, 7, 1504; e) H.
P. Du, H. Yang, C. S. Huang, J. J. He, H. B. Liu, Y. L. Li, Nano Energy 2016, 22,
615 ; f) Y. Xu, M. Kraft, R. Xu, Chem. Soc. Rev. 2016, 45, 3039; g) Q. Lv, W. Y. Si,
Z. Yang, N. Wang, Z. Y. Tu, Y. P. Yi, C. S. Huang, L. Jiang, M. J. Zhang, J. J. He, Y.
Z. Long, Acs Appl. Mater. Interfaces 2017, 9, 29744; h) Q. Lv, W. Y. Si, J. J. He, L.
Sun, C. F. Zhang, N. Wang, Z. Yang, X. D. Li, X. Wang, W. Q. Deng, Y. Z. Long, C.
S. Huang, Y. L. Li, Nat. Commun. 2018, 9; i) Y. R. Xue, Y. L. Li, J. Zhang, Z. F. Liu,
Y. L. Zhao, Sci. China Chem. 2018, 61, 765; j) Y. S. Zhao, J. W. Wan, H. Y. Yao, L. J.
Zhang, K. F. Lin, L. Wang, N. L. Yang, D. B. Liu, L. Song, J. Zhu, L. Gu, L. Liu, H. J.
Zhao, Y. L. Li, D. Wang, Nat. Chem. 2018, 10, 924; k) T. He, S. K. Matta, G. Will, A.
Du, Small Methods 2019, 0, 1800419.
[4]
a) G. X. Li, Y. L. Li, H. B. Liu, Y. B. Guo, Y. J. Li, D. B. Zhu, Chem. Commun. 2010,
46, 3256; b) B. Wu, M. R. Li, S. N. Xiao, Y. K. Qu, X. Y. Qiu, T. F. Liu, F. H. Tian,
H. X. Li, S. X. Xiao, Nanoscale 2017, 9, 11939; c) S. Kim, D. Thirion, T. S. Nguyen,
B. Kim, N. A. Dogan, C. T. Yavuz, Chem. Mater. 2019, 31, 5206; d) D. Schwarz, Y.
Noda, J. Klouda, K. Schwarzova-Peckova, J. Tarabek, J. Rybacek, J. Janousek, F.
Simon, M. V. Opanasenko, J. Cejka, A. Acharjya, J. Schmidt, S. Selve, V. Reiter-
Scherer, N. Severin, J. P. Rabe, P. Ecorchard, J. J. He, M. Polozij, P. Nachtigall, M. J.
Bojdys, Adv. Mater. 2017, 29; e) H. Shang, Z. C. Zuo, H. Y. Zheng, K. Li, Z. Y. Tu, Y.
P. Yi, H. B. Liu, Y. J. Li, Y. L. Li, Nano Energy 2018, 44, 144; f) Y. W. Song, X. D.
Li, Z. Yang, J. Wang, C. Y. Liu, C. P. Xie, H. L. Wang, C. S. Huang, Chem. Commun.
2019, 55, 6571; g) Z. Yang, R. R. Liu, N. Wang, J. J. He, K. Wang, X. D. Li, X. Y.
Shen, X. Wang, Q. Lv, M. J. Zhang, J. Luo, T. G. Jiu, Z. F. Hou, C. S. Huang, Carbon
2018, 137, 442.
[5]
a) C. N. Ge, J. Chen, S. L. Tang, Y. W. Du, N. J. Tang, Acs Appl. Mater. Interfaces
2019, 11, 2707; b) J. Y. Zhou, X. Gao, R. Liu, Z. Q. Xie, J. Yang, S. Q. Zhang, G. M.
Zhang, H. B. Liu, Y. L. Li, J. Zhang, Z. F. Liu, J. Am. Chem. Soc. 2015, 137, 7596; c)
X. Gao, J. Y. Zhou, R. Du, Z. Q. Xie, S. B. Deng, R. Liu, Z. F. Liu, J. Zhang, Adv.
Mater. 2016, 28, 168; d) X. Gao, J. Li, R. Du, J. Y. Zhou, M. Y. Huang, R. Liu, J. Li,
Z. Q. Xie, L. Z. Wu, Z. F. Liu, J. Zhang, Adv. Mater. 2017, 29, 1605308; e) Y.J. Li, L.
Xu, H. B. Liu, Y. L. Li, Chem. Soc. Rev. 2014, 43, 2572; f) Y. J. Li, T. F. Liu, H. B.
17
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
Liu, M. Z. Tian, Y. L. Li, Acc. Chem. Res. 2014, 47, 1186; g) Z. Y. Jia, Y. J. Li, Z. C.
Zuo, H. B. Liu, C. S. Huang, Y. L. Li, Acc. Chem. Res. 2017, 50, 2470; h) Y. R. Xue,
B. L. Huang, Y. P. Yi, Y. Guo, Z. C. Zuo, Y. J. Li, Z. Y. Jia, H. B. Liu, Y. L. Li, Nat.
Commun. 2018, 9, 1460. i) L. Hui, Y. R. Xue, B. L. Huang, H. D. Yu, C. Zhang, D. Y.
Zhang, D. Z. Jia, Y. J. Zhao, Y. G. Li, H. B. Liu, Y. L. Li, Nat. Commun. 2018, 9,
5309; j) Q. Lv, W. Y. Si, J. J. He, L. Sun, C. F. Zhang, N. Wang, Z. Yang, X. D. Li, X.
Wang, W. Q. Deng, Y. Z. Long, C. S. Huang, Y. L. Li, Nat. Commun. 2018, 9, 3376.
k) W. H. Zhou, T. Han, H. D. Cui, Z. Zhao, P. K. Chu, X. F. Yu, Angew. Chem. Int.
Ed. 2018, 57, 774; l) C. Lu, Y. Yang, J. Wang, R. P. Fu, X. X. Zhao, L. Zhao, Y. Ming,
Y. Hu, H. Z, Lin, X. M. Tao, Y. L. Li, W. Chen, Nat. Commun. 2018, 9, 752.
[6]
[7]
a) M. H. Sun, S. Z. Huang, L. H. Chen, Y. Li, X. Y. Yang, Z. Y. Yuan, B. L. Su,
Chem. Soc. Rev. 2016, 45, 3479; b) X. W. Wang, G. Z. Sun, P. Routh, D. H. Kim, W.
Huang, P. Chen, Chem. Soc. Rev. 2014, 43, 7067; c) Y. H. Xue, Q. Zhang, W. J. Wang,
H. Cao, Q. H. Yang, L. Fu, Adv. Energy Mater. 2017, 7.
a) T. Chen, W. Q. Li, W. B. Hu, W. J. Hu, Y. H. A. Liu, H. Yang, K. Wen, Rsc Adv.
2019, 9, 18008; b) Q. G. Pan, T. Chen, L. S. Ma, G. L. Wang, W. B. Hu, Z. Q. Zou, K.
Wen, H. Yang, Chem. Mater. 2019, 31, 8062.
[8]
[9]
Z. A. Lan, Y. X. Fang, Y. F. Zhang, X. C. Wang, Angew. Chem. Int. Ed. 2018, 57, 470.
M. Juricek, M. Felici, P. Contreras-Carballada, J. Lauko, S. R. Bou, P. H. J. Kouwer,
A. M. Brouwer, A. E. Rowan, J. Mater. Chem. 2011, 21, 2104.
[10] a) D. C. Wei, Y. Q. Liu, Y. Wang, H. L. Zhang, L. P. Huang, G. Yu, Nano Lett. 2009,
9, 1752; b) Z. H. Xiang, D. P. Cao, L. Huang, J. L. Shui, M. Wang, L. M. Dai, Adv.
Mater. 2014, 26, 3315.
[11] K. W. Wang, L. M. Yang, X. Wang, L. P. Guo, G. Cheng, C. Zhang, S. B. Jin, B. Tan,
A. Cooper, Angew. Chem. Int. Ed. 2017, 56, 14149.
[12] K. A. Cychosz, R. Guillet-Nicolas, J. Garcia-Martinez, M. Thommes, Chem. Soc. Rev.
2017, 46, 389.
[13] M. Otsuka, Powder Technol. 2004, 141, 244.
[14] S. Bai, J. Jiang, Q. Zhang, Y. J. Xiong, Chem. Soc. Rev. 2015, 44, 2893.
[15]
a) S. T. Kochuveedu, Y. H. Jang, D. H. Kim, Chem. Soc. Rev., 2013, 42, 8467; b) P.
Ganguly, C. Byrne, A. Breen, S. C. Pillai, Appl. Catal. B-Environ. 2018, 225, 51.
[16] H. M. Wang, C. F. You, Z. C. Tan, Chem. Eng. J. 2018, 350, 89.
[17] a) R. Cai, B. Zhang, J. Shi, M. Li, Z. He, ACS Sustainable Chem. Eng.,2017, 5, 7690;
b) N. Baliarsingh, K. M. Parida, G. C. Pradhan, Ind. Eng. Chem. Res. 2014, 53, 3834;
c) L. C. Chen, T. C, Chou, Ind. Eng. Chem. Res. 1994, 33, 1436; d) N. Bao, X. Feng,
Z. Yang, L. Shen, X. Lu, Environ. Sci. Technol. 2004, 38, 2729; e) W. Li, D. Li, J.
Xian, W. Chen, Y. Hu, Y. Shao, X. Fu, J. Phys. Chem. C, 2010, 114, 21482; f) W. Li,
D. Li, Y. Lin, P. Wang, W. Chen, X. Fu, Y. Shao, J. Phys. Chem. C, 2012, 116, 3552;
g) A. Petrella, M. Petrella, G. Boghetich, P. Mastrorilli, V. Petruzzelli, E. Ranieri, D.
18
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
Petruzzelli, Ind. Eng. Chem. Res., 2013, 52, 2201; h) B. Dindar, S. Içli, J. Photochem.
Photobio. A: Chem. 2010,140, 263; i) Y. Yang, G. Wang, Q. Deng, D. H. L. Ng, H.
Zhao, ACS Appl. Mater. Interfaces, 2014, 6, 3008; j) Z. Chen, F. Bing, Q. Liu, Z.
Zhang, X. Fang, J. Mater. Chem. A, 2015, 3, 4652; k) L. Jiang, X. Yuan, G. Zeng, X.
Chen, Z. Wu, J. Liang, J. Zhang, H. Wang, H. Wang, ACS sustainable Chem. Eng.
2017, 5, 5831; l) S. Ahmed, M. G. Rasul, R. Brown, M. A. Hashib, J. Environ.
Manage., 2011, 92, 311; m) B. Sun, H. Li, X. Li, X. Liu, C. Zhang, H. Xu, X. S. Zhao,
Int. Eng. Chem. Res., 2018, 57, 14011.
[18] N. Panda, H. Sahoo, S. Mohapatra, J. Hazard. Mater. 2011, 185, 359.
[19] T. A. Saleh, A. A. Al-Saadi, V. K. Gupta, J. Mol. Liq., 2014, 191, 85.
[20] G. Calogero, A. Bartolotta, G. D. Marco. A. D. Carlo, F. Bonaccorso, Chem. Soc. Rev.,
2015, 44, 3244.
[21] B. O. Okesola, D. K. Smith, Chem. Soc. Rev. 2016, 45, 4226.
[22] World Health Organization, Guidelines for Drinking-water Quality, 2017.
[23] Z. Y. Teng, N. L. Yang, H. Y. Lv, S. C. Wang, M. Z. Hu, C. Y. Wang, D. Wang, G. X.
Wang, Chem 2019, 5, 664.
[24] a)Z. Wang, C. Li, K. Domen, Chem. Soc. Rev. 2019, 48, 2109; b) C. Liu, D. S. Kong,
P. C. Hsu, H. T. Yuan, H. W. Lee, Y. Y. Liu, H. T. Wang, S. Wang, K. Yan, D. C. Lin,
P. A. Maraccini, K. M. Parker, A. B. Boehm, Y. Cui, Nat. Nanotechnol. 2016, 11,
1098; c) Y. N. Zhang, W. X. Liu, Y. J. Li, Y. W. Yang, A. Dong, Y. L. Li, iScience,
2019, 662.
[25] a) P. Yadav, S. T. Nishanthi, B. Purohit. A. Shanavas, K. Kailasam, Carbon 2019, 152,
587. b) J. S. Kim, E. Kuk, K. N. Yu, J.-H. Kim, S. J.. Park, H. J. Lee, S. H. Kim, Y. K.
Park, Y. H. Park, C.-Y. Hwang, Y.-K. Kim, Y.-S. Lee, D. H. Jeong, M.-H. Cho,
Nanomed. Nanotechnol. Biol. Med. 2007, 1, 95.
19
This article is protected by copyright. All rights reserved.

10.1002/chem.201905133
Chemistry - A European Journal
A new N-doped graphyne analog, triazine- and 1,4-diethynylbenzene-based graphyne (TA-
BGY), was synthesized through aromatic nucleophilic substitution reactions.TA-BGY was
expected to have many applications which were exampled by the photodegradation of methyl
orange (99%) and photocatalytic bacterial inactivation (Escheichia coli, under 1h irradiation
of simulated sunlight, AM 1.5G, 100 mW/cm2, no live bacterium was detected).
Keyword: graphyne analog, aromatic nucleophilic substitution reaction, hydroxyl radical,
photocatalytic dye degradation, antibiosis
Tao Chen, Wen-Qian Li, Xiao-Jia Chen, Yun-Zhe Guo, Wei-Bo Hu*, Wen-Jing Hu, Yahu A.
Liu, Hui Yang* and Ke Wen*
A Novel Triazine-Based Analog of Graphyne: Scalable Synthesis and Applications in
Photocatalytic Dye Degradation and Bacterial Inactivation
ToC figure ((Please choose one size: 55 mm broad × 50 mm high or 110 mm broad × 20 mm
high. Please do not use any other dimensions))
55 mm broad × 50 mm high
20
This article is protected by copyright. All rights reserved.