Benzobisthiazole-based Regioisomeric Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production

Ruo-Fan Li; Ran Huo; Zhao-Hui Zhang; Yong-Chao Lu; Pei Fan; Xuan Zhang; Tan Su; Qiao-Lin Wu; Long Chen

doi:10.1007/s10118-025-3551-z

Your Location：

Home >

Browse articles >

Benzobisthiazole-based Regioisomeric Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production

RAPID COMMUNICATION | Updated：2026-04-30

- Benzobisthiazole-based Regioisomeric Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production
- Benzobisthiazole-based Regioisomeric Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production
- Chinese Journal of Polymer Science 2026年44卷第5期页码：1201-1211
- Affiliations：
  
  a.State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
  b.Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China
- Author bio：
  
  sutan_jlu@jlu.edu.cn (T.S.)
  wuql@jlu.edu.cn (Q.L.W.)
  longchen@jlu.edu.cn (L.C.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52473211) and the Science and Technology Development Plan Project of Changchun, China (No. 2024GZZ03).;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3551-z.The data supporting the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-025-3551-z
  中图分类号：
- 收稿：2025-12-02，
  
  录用：2025-12-29，
  
  网络首发：2026-04-03，
  
  纸质出版：2026-05-05
- Accepted：
Scan QR Code
Li, R. F.; Huo, R.; Zhang, Z. H.; Lu, Y. C.; Fan, P.; Zhang, X.; Su, T.; Wu, Q. L.; Chen, L. Benzobisthiazole-based regioisomeric donor-acceptor covalent organic frameworks for photocatalytic hydrogen peroxide production. Chinese J. Polym. Sci. 2026, 44, 1201–1211

Ruo-Fan Li, Ran Huo, Zhao-Hui Zhang, et al. Benzobisthiazole-based Regioisomeric Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1201-1211.
Li, R. F.; Huo, R.; Zhang, Z. H.; Lu, Y. C.; Fan, P.; Zhang, X.; Su, T.; Wu, Q. L.; Chen, L. Benzobisthiazole-based regioisomeric donor-acceptor covalent organic frameworks for photocatalytic hydrogen peroxide production. Chinese J. Polym. Sci. 2026, 44, 1201–1211 DOI： 10.1007/s10118-025-3551-z.

Ruo-Fan Li, Ran Huo, Zhao-Hui Zhang, et al. Benzobisthiazole-based Regioisomeric Donor-Acceptor Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1201-1211. DOI： 10.1007/s10118-025-3551-z.

摘要

Two regioisomeric benzobisthiazole (BT)-based covalent organic frameworks (COFs) are constructed

via

molecular isomerization. The 2

6-BT-COF exhibits a superior H

production rate of 1638 μmol·g

–1

·h

–1

in pure water under visible light

demonstrating the crucial role of molecular connectivity in boosting photocatalytic charge separation.

Abstract

This study develops an effective molecular isomerization strategy to enhance photocatalytic hydrogen peroxide (H

) production by leveraging the structural tunability of benzobisthiazole (BT)―an electron-deficient planar heterocycle with superior optoelectronic properties and chemical stability. Unlike conventional isomeric covalent organic frameworks (COFs) which focus on symmetric or unidirectional conjugation systems

we exploit the two orthogonal

-conjugation pathways (2

6- versus 4

8-substitution) of BT to construct regioisomeric COFs with distinct topological connectivity

a design that remains rarely explored for photocatalytic H

generation. Utilizing subsitution-position flexibility of BT

two regioisomeric monomers

namely 2

6-BT-CHO and 4

8-BT-CHO

pro

were designed and polymerized into highly crystalline donor-acceptor (D-A) covalent organic frameworks (COFs): 2

6-BT-COF and 4

8-BT-COF. These COFs exhibit high surface areas

extended

-conjugation

and excellent light-harvesting capabilities

endering them ideal photocatalysts. Remarkably

under visible-light irradiation in pure water

6-BT-COF achieved a H

production rate of 1638 μmol·g

–

·h

–

outperforming 4

8-BT-COF (1046 μmol·g

–

·h

–

) by about 57%. Structural and photophysical analyses reveal that this pronounced performance difference stems from the critical influence of molecular topology on charge separation

exciton dissociation

and redox kinetics. Specifically

6-BT-COF facilitates more efficient intramolecular charge transfer and suppresses charge recombination losses compared its 4

8-substituted counterpart. This work not only presents two novel

structurally well-defined COF photocatalysts but also establishes a design principle for optimizing photocatalytic efficiency through precise control of molecular connectivity.

关键词

Keywords

references

Campos-Martin, J. M.; Blanco-Brieva, G.; Fierro, J. L. G. Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. Angew. Chem. Int. Ed. 2006 , 45 , 6962−6984..

Hage, R.; Lienke, A. Applications of transition-metal catalysts to textile and wood-pulp bleaching. Angew. Chem. Int. Ed. 2005 , 45 , 206−222..

Gurram, R. N.; Al-Shannag, M.; Lecher, N. J.; Duncan, S. M.; Singsaas, E. L.; Alkasrawi, M. Bioconversion of paper mill sludge to bioethanol in the presence of accelerants or hydrogen peroxide pretreatment. Bioresour. Technol. 2015 , 192 , 529−539..

Richards, T.; Harrhy, J. H.; Lewis, R. J.; Howe, A. G. R.; Suldecki, G. M.; Folli, A.; Morgan, D. J.; Davies, T. E.; Loveridge, E. J.; Crole, D. A.; Edwards, J. K.; Gaskin, P.; Kiely, C. J.; He, Q.; Murphy, D. M.; Maillard, J.-Y.; Freakley, S. J.; Hutchings, G. J. A residue-free approach to water disinfection using catalytic in situ generation of reactive oxygen species. Nat. Catal. 2021 , 4 , 575−585..

Zhao, Y.; Sun, M.; Wang, X.; Wang, C.; Lu, D.; Ma, W.; Kube, S. A.; Ma, J.; Elimelech, M. Janus electrocatalytic flow-through membrane enables highly selective singlet oxygen production. Nat. Commun. 2020 , 11 , 6228..

Ksibi, M. Chemical oxidation with hydrogen peroxide for domestic wastewater treatment. Chem. Eng. J. 2006 , 119 , 161−165..

Zhan, W.; Ji, L.; Ge, Z.-m.; Wang, X.; Li, R.-t. A continuous-flow synthesis of primary amides from hydrolysis of nitriles using hydrogen peroxide as oxidant. Tetrahedron 2018 , 74 , 1527−1532..

Mase, K.; Yoneda, M.; Yamada, Y.; Fukuzumi, S. Seawater usable for production and consumption of hydrogen peroxide as a solar fuel. Nat. Commun. 2016 , 7 , 11470..

Hou, H.; Zeng, X.; Zhang, X. Production of hydrogen peroxide by photocatalytic processes. Angew. Chem. Int. Ed. 2020 , 59 , 17356−17376..

Yang, S.; Verdaguer-Casadevall, A.; Arnarson, L.; Silvioli, L.; Čolić, V.; Frydendal, R.; Rossmeisl, J.; Chorkendorff, I.; Stephens, I. E. L. Toward the decentralized electrochemical production of H 2 O 2 : a focus on the catalysis. ACS Catal. 2018 , 8 , 4064−4081..

Chen, D.; Chen, W.; Wu, Y.; Wang, L.; Wu, X.; Xu, H.; Chen, L. Covalent organic frameworks containing dual O 2 reduction centers for overall photosynthetic hydrogen peroxide production. Angew. Chem. Int. Ed. 2023 , 62 , e202217479..

Zhang, Z.; Xu, Y. Hydrothermal synthesis of highly crystalline zwitterionic vinylene-linked covalent organic frameworks with exceptional photocatalytic properties. J. Am. Chem. Soc. 2023 , 145 , 25222−25232..

Huang, Q. Q.; Li, N.; Han, M. S.; Liu, J.; Lan, Y. Q. Conductive knitting of covalent organic framework manipulates spin density, orbital reorganization, and charge mobility for outstanding photoreactivity. Angew. Chem. Int. Ed. 2025 , 64 , e202513848..

Xu, Q.; Han, J.; Tian, F.; Zhao, X.; Rong, J.; Zhang, J.; She, P.; Qin, J.-S.; Rao, H. Synergistic bifunctional covalent organic framework for efficient photocatalytic CO 2 reduction and water oxidation. J. Am. Chem. Soc. 2025 , 147 , 10587−10597..

Sun, L.; Lu, M.; Yang, Z.; Yu, Z.; Su, X.; Lan, Y. Q.; Chen, L. Nickel glyoximate based metal-covalent organic frameworks for efficient photocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 2022 , 61 , e202204326..

Chen, Y.; Guo, Y.; Wang, T.; Ji, S.; Shao, H.; Lin, M.; Seki, S.; Yan, N.; Jiang, D. Covalent organic framework photocatalysts for green and efficient photochemical transformations. Nat. Commun. 2025 , 16 , 6495..

Kou, M.; Wang, Y.; Xu, Y.; Ye, L.; Huang, Y.; Jia, B.; Li, H.; Ren, J.; Deng, Y.; Chen, J.; Zhou, Y.; Lei, K.; Wang, L.; Liu, W.; Huang, H.; Ma, T. Molecularly engineered covalent organic frameworks for hydrogen peroxide photosynthesis. Angew. Chem. Int. Ed. 2022 , 61 , e202200413..

[Zhang, F.; Lv, X.; Wang, H.; Cai, J.; Wang, H.; Bi, S.; Wei, R.; Yang, C.; Zheng, G.; Han, Q. p-π Conjugated covalent organic frameworks expedite moleculartriplet excitons for H 2 O 2 production coupled with biomass upgrading. Adv. Mater . 2025 , 37 , 2502220..

Jiang, R.; Wang, X.; Shi, C.; Li, Y.; Xu, Q.; Yang, X.; Li, C.; Liu, C.; Liu, Z.; Wang, K.; Jiang, J.; Feng, Y. Piperazine-linked phthalocyanine covalent organic frameworks for efficient anodic lithium storage. ACS Appl. Mater. Interfaces 2025 , 17 , 24005−24013..

Li, H.; Fan, J.; Ran, M.; Borse, R. A.; Lin, S.-X.; Yuan, D. Design and construction of D–A-extended 3D covalent-organic frameworks for boosting photocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 2025 , 64 , e202500937..

[Guo, J.; Zhong, X.-H.; Rao, L.; Wang, B.-Z.; Chen, Z.; Zhang, Y.; Wu, T.; Carabineiro, S. A. C.; Wen, L.-L.; Duan, C.-Y. Anthraquinone-based donor–acceptor covalent organic frameworks with thiazole linkages to enhance direct hydrogen atom transfer and charge separation in photocatalytic oxidation of C(sp 3 )-H bonds. Angew. Chem. Int. Ed . 2025 , e202517694..

Liu, C.; Liu, X.; Chen, B.; Li, Z.; Ou, X.; Lu, Y.; Liu, Y.; Wu, C.; Yao, S.; Liu, Y.; Ye, L.; Han, B.; Yang, Z. Squaric acid-based zwitterionic covalent organic framework induces triple synergy for boosted hydrogen peroxide photosynthesis. Nat. Commun. 2025 , 16 , 8941..

Chen, J.; Zhang, X.; Cai, X. ; Ni, Y.; Bai, F.; Chen, Y.; Wang, H. Design of donor–acceptor type 2D covalent organic frameworks as efficient photocatalysts for visible-light-driven water splitting. Adv. Funct. Mater. 2025 , 35 , 2505453..

Chen, Z.; Guo, J.; Song, F. H.; Wang, S. D.; Carabineiro, S. A. C.; Ouyang, S. X.; Wen, L. L. Rational regulation of dipole polarization in donor–acceptor covalent organic frameworks for enhanced photocatalytic efficiency. ACS Catal. 2025 , 15 , 8284−8296..

Luan, T.-X.; Xing, L.-B.; Lu, N.; Li, X.-L.; Kong, S.; Yu, W. W.; Li, P.-Z.; Zhao, Y. Donor–acceptor–π–acceptor–donor-type photosensitive covalent organic framework for effective photocatalytic aerobic oxidation. J. Am. Chem. Soc. 2025 , 147 , 12704−12714..

[Cao, D.; Gong, C.; Han, Y.; Zhu, C.; Ma, Y.; Xia, Q.; Peng, Y.; Yuan, G. Engineering donor–acceptor arrangement in perylene diimide-based covalent organic frameworks for enhanced singlet oxygen photocatalysis. Angew. Chem. Int. Ed . 2025 , e202516908..

Tang, W.; Zeng, J.; Bian, F.; Lin, H.; Zhao, H.; Lu, Z. Y. Engineering heteroatomic structures in Pt single-atom anchored covalent organic frameworks for enhanced photocatalytic hydrogen evoluti on reaction. J. Mater. Chem. A. 2025 , 13 , 19682−19694..

Yang, J.; Zhao, Z.; Liu, X.; Yang, H.; Yang, J.; Zhou, M.; Li, S.; Liu, X.; Xu, X.; Cheng, C. Homologous heteropolyaromatic covalent organic frameworks for enhancing photocatalytic hydrogen peroxide production and aerobic oxidation. Nat. Commun. 2025 , 16 , 7654..

Ju, Y.; Lin, H.; Tan, G.; Su, P.; Wang, Z.; Hu, C.; Hou, R.; Hao, T.; Chen, F.; Tang, Y. Regulating the electronic structure of covalent organic frameworks via heterocyclic isomers for highly efficient photocatalytic H 2 O 2 generation. Nat. Commun. 2025 , 16 , 5658..

Yang, M. Y.; Zhang, S. B.; Zhang, M.; Li, Z. H.; Liu, Y. F.; Liao, X.; Lu, M.; Li, S. L.; Lan, Y. Q. Three-motif molecular junction type covalent organic frameworks for efficient photocatalytic aerobic oxidation. J. Am. Chem. Soc. 2024 , 146 , 3396−3404..

He, Y.; Zhao, Y.; Wang, X.; Liu, Z.; Yu, Y.; Li, L. Multiple heteroatom-hydrogen bonds bridging electron transport in covalent organic framework-based supramolecular system for photoreduction of CO 2 . Angew. Chem. Int. Ed. 2023 , 62 , e202307160..

Qian, Y.; Jiang, H. L. Structural regulation of covalent organic frameworks for catalysis. Acc. Chem. Res. 2024 , 57 , 1214−1226..

Zhou, E.; Wang, F.; Zhang, X.; Hui, Y.; Wang, Y. Cyanide-based covalent organic frameworks for enhanced overall photocatalytic hydrogen peroxide production. Angew. Chem. Int. Ed. 2024 , 63 , e202400999..

Yang, H.; Zhao, R.; Wang, J.; Yin, X.; Lu, Z.; Hou, L. Local electron donor defects induce dipole polarization boosting on covalent organic frameworks to promote photocatalysis. ACS Mater. Lett. 2023 , 5 , 2877−2886..

He, H.-X.; Zhang, C. R.; Chen, X.-J.; Liang, R.-P.; Qiu, J.-D. Reconstruction of built-in electric field in covalent organic frameworks through defect engineering for photocatalytic reduction of uranium. ACS Appl. Polym. Mater. 2025 , 7 , 4525−4534..

[Ding, X.; Wang, T.; Yu, B.; Zhi, Q.; Wang, H.; Liu, H.; Stuzhin, P. A.; Jiang, J. 10% Conversion of imine into thiazole in covalent organic frameworks for efficient photocatalytic H 2 O 2 generation. Adv. Funct. Mater . 2025 , 35 , 2422291..

Du, K.; Xiong, L.; Fu, C.; Ni, X.; Bredas, J.-L.; Li, H. Impact of structural defects on the electronic properties of two-dimensional covalent organic frameworks. ACS Mater. Lett. 2024 , 6 , 335−344..

Yang, C.; Le, J.; Kuang, Y.; Meng, Z.; Dai, H.; Zhou, Y.; Qiu, H. Quasi-one-dimensional zigzag covalent organic frameworks for photocatalytic hydrogen evolution from water. J. Am. Chem. Soc. 2024 , 146 , 26198−26206..

Bian, R.; Deng, Y.; Li, Y.; Li, P.; Gao, R.; Luo, Y.; Lu, J.; Fan, C.; Liu, L.; Xia, Z.; Wu, X. Inducing exciton dissociation in covalent organic framework by local gradient ionic polarization for enhanced hydrogen peroxide photosynthesis. Appl. Catal. B: Environ. Energy 2025 , 371 , 125292..

Qi, J. X.; Gong, J. W.; Peng, Z. H.; Zhang, C. R.; Liu, J. L.; Cai, Y. J.; Chen, X. J.; Wang, X. X.; Liang, R. P.; Qiu, J. D. Defect engineering enhancing piezoelectric catalytic activity of covalent organic framework matrix composites for uranium removal. Small 2025 , 21 , 2409682..

Wang, W.; Zhang, R.; Chu, H.; Zhan, Z.; Huang, Q.; Li, Z.; Wang, X.; Bai, F.; Zhou, W. Isomerization of covalent organic frameworks for efficiently activating molecular oxygen and promoting hydrogen peroxide photosynthesis. Small 2025 , 21 , 2406527..

Li, S.; Ma, R.; Xu, S.; Zheng, T.; Fu, G.; Wu, Y.; Liao, Z.; Kuang, Y.; Hou, Y.; Wang, D.; Petkov, P. S.; Simeonova, K.; Feng, X.; Wu, L.Z.; Li, X. B.; Zhang, T. Direct construction of isomeric benzobisoxazole–vinylene-linked covalent organic frameworks with distinct photocatalytic properties. J. Am. Chem. Soc. 2022 , 144 , 13953−13960..

Ren, X.; Wen, M.; Hou, X.; Sun, J.; Bai, F.; Li, Y. Covalent organic framework isomers with divergent photocatalytic properties. Chem. Commun. 2024 , 60 , 4423−4426..

Zhang, W.; Sun, M.; Cheng, J.; Wu, X.; Xu, H. Regulating electron distribution in regioisomeric covalent organic frameworks for efficient solar-driven hydrogen peroxide production. Adv. Mater. 2025 , 37 , 2500913..

Wang, W. Z.; Tian, P. J.; Fu, Y.; Wan, X.; Lei, X.; Jia, C.; Liu, C.; Qi, Q. Y.; Xu, S. Q.; Zhao, X. Orthorhombic covalent organic frameworks with fmj topology as ph otocatalyst for hydrogen evolution. Angew. Chem. Int. Ed. 2025 , 64 , e202418086..

Hu, Y.; Ding, X.; Feng, J.; Yan, Y.; Shao, C.; Yu, X.; Shao, J.; Ji, Y.; Li, Y.; Huang, W.; Li, Y. Molecular regioisomerism of benzobisthiazole-based conjugated polymers promotes photocatalytic hydrogen production. Adv. Funct. Mater. 2024 , 34 , 2400946..

Chen, W.; Wang, L.; Mo, D.; He, F.; Wen, Z.; Wu, X.; Xu, H.; Chen, L. Modulating benzothiadiazole-based covalent organic frameworks via halogenation for enhanced photocatalytic water splitting. Angew. Chem. Int. Ed. 2020 , 59 , 16902−16909..

Li, S.; Ma, R.; Tu, C.; Zhang, W.; Li, R.; Zhao, Y.; Zhang, K. A. I. Programmed charge transfer in conjugated polymers with pendant benzothiadiazole acceptor for simultaneous photocatalytic H 2 O 2 production and organic synthesis. Angew. Chem. Int. Ed. 2025 , 64 , e202421040..

Fu, G.; Yang, D.; Xu, S.; Li, S.; Zhao, Y.; Yang, H.; Wu, D.; Petkov, P. S.; Lan, Z. A.; Wang, X.; Zhang, T. Construction of thiadiazole-bridged sp 2 -carbon-conjugated covalent organic frameworks with diminished excitation binding energy toward superior photocatalysis. J. Am. Chem. Soc. 2024 , 146 , 1318−1325..

[Wang, Y.; Zhao, X.; Han, G.; Bi, J.; Zhao, Y. Facile construction of fully conjugated benzotristhiazole-based covalent organic frameworks for efficient photocatalytic H 2 O 2 production. Adv. Funct. Mater . 2025 , 2508550..

Liu, P.; Liang, T.; Li, Y.; Zhang, Z.; Li, Z.; Bian, J.; Jing, L. Photocatalytic H 2 O 2 production over boron-doped g-C 3 N 4 containing coordinatively unsaturated FeOOH sites and CoO x clusters. Nat. Commun. 2024 , 15 , 9224..

Ren, P.; Zhang, T.; Jain, N.; Ching, H. Y. V.; Jaworski, A.; Barcaro, G.; Monti, S.; Silvestre-Albero, J.; Celorrio, V.; Chouhan, L.; Rokicińska, A.; Debroye, E.; Kuśtrowski, P.; Van Doorslaer, S.; Van Aert, S.; Bals, S.; Das, S. An atomically dispersed Mn-photocatalyst for generating hydrogen peroxide from seawater via the water oxidation reaction (WOR). J. Am. Chem. Soc. 2023 , 145 , 16584−16596..

Huang, W.; Hu, Y.; Qin, Z.; Ji, Y.; Zhao, X.; Wu, Y.; He, Q.; Li, Y.; Zhang, C.; Lu, J.; Li, Y. Highly crystalline and water-wettable benzobisthiazole-based covalent organic frameworks for enhanced photocatalytic hydrogen production. Nat. Sci. Rev. 2023 , 10 , nwac171..

浏览量

742

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Managing Interpenetration in 3D Covalent Organic Frameworks with Spatial-aromatic Building Blocks

A Pyrazine-based Covalent Organic Framework as a Cathode Material for Aqueous Rechargeable Zinc-ion Batteries

Covalent Organic Framework/Carbon Nanotube Composites for Enhanced Lithium-ion Battery Performance

Toward High-crystalline Covalent Organic Framework via Dynamic Condensation of Carbon-Carbon Double Bond

Covalent Organic Frameworks Modified Composite Proton Exchange Membranes towards Advanced Fuel Cells