Topologically Isomeric Effects on the Photocatalytic H<sub>2</sub>O<sub>2</sub> Production Performance of Two-dimensional Covalent Organic Frameworks

Xing Su; Yi-Xue Xu; Chao Liu; Peng-Ju Tian; Ya Lu; Mei-Mei Zhang; Shun-Feng Li; Meng-Jing Sun; Fan Qiu; Yu-Qiao Wang; Yu-Bin Fu; Shun-Qi Xu; Xin Zhao

doi:10.1007/s10118-026-3602-0

Your Location：

Home >

Browse articles >

Topologically Isomeric Effects on the Photocatalytic H₂O₂ Production Performance of Two-dimensional Covalent Organic Frameworks

RESEARCH ARTICLE | Updated：2026-04-30

- Topologically Isomeric Effects on the Photocatalytic H₂O₂ Production Performance of Two-dimensional Covalent Organic Frameworks
- Chinese Journal of Polymer Science Vol. 44, Issue 5, Pages: 1403-1410(2026)
- Affiliations：
  
  a.Key Lab of Functional Polymers for Sustainability of Jiangsu, School of Energy and Environment, Southeast University, Nanjing 211189, China
  b.Research Center for Nano Photoelectrochemistry and Devices, School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China
  c.The Institute for Advanced Studies, Hubei Key Lab on Organic and Polymeric Opto-Electronic Materials, Wuhan University, Wuhan 430072, China
- Author bio：
  
  shunqi.xu@seu.edu.cn (S.Q.X.)
  xin-zhao@seu.edu.cn (X.Z.)
- Funds：
- DOI：10.1007/s10118-026-3602-0
  CLC：
- Received：07 January 2026，
  
  Accepted：29 January 2026，
  
  Online First：09 April 2026，
  
  Published：05 May 2026
- Accepted：
Scan QR Code
Su, X.; Xu, Y. X.; Liu, C.; Tian, P. J.; Lu, Y.; Zhang, M. M.; Li, S. F.; Sun, M. J.; Qiu, F.; Wang, Y. Q.; Fu, Y. B.; Xu, S. Q.; Zhao, X. Topologically isomeric effects on the photocatalytic H₂O₂ production performance of two-dimensional covalent organic frameworks. Chinese J. Polym. Sci. 2026, 44, 1403–1410 DOI: 10.1007/s10118-026-3602-0.

Xing Su, Yi-Xue Xu, Chao Liu, et al. Topologically Isomeric Effects on the Photocatalytic H₂O₂ Production Performance of Two-dimensional Covalent Organic Frameworks[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1403-1410. DOI: 10.1007/s10118-026-3602-0.
Su, X.; Xu, Y. X.; Liu, C.; Tian, P. J.; Lu, Y.; Zhang, M. M.; Li, S. F.; Sun, M. J.; Qiu, F.; Wang, Y. Q.; Fu, Y. B.; Xu, S. Q.; Zhao, X. Topologically isomeric effects on the photocatalytic H₂O₂ production performance of two-dimensional covalent organic frameworks. Chinese J. Polym. Sci. 2026, 44, 1403–1410 DOI: 10.1007/s10118-026-3602-0. DOI：

Xing Su, Yi-Xue Xu, Chao Liu, et al. Topologically Isomeric Effects on the Photocatalytic H₂O₂ Production Performance of Two-dimensional Covalent Organic Frameworks[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1403-1410. DOI: 10.1007/s10118-026-3602-0. DOI：

摘要

Topological isomers of 2D covalent organic frameworks (COFs) with

kgm

and

sql

topologies

derived from identical building blocks

reveal a distinct topology-property relationship in photophysical properties and photocatalytic performance.

Abstract

Two-dimensi

onal covalent organic frameworks (2D COFs)

characterized by tunable optoelectronic properties and well-defined porous architectures

have emerged as promising photocatalysts for solar-driven H

production. Although network topology exerts a profound impact on the optoelectronic characteristics of 2D materials

achieving precise regulation of their topology remains a significant challenge. In this study

we report two topologically isomeric 2D COFs constructed from the same building blocks

namely ETBA-

kgm

-COF with a

kgm

topology and ETBA-

sql

-COF with a

sql

topology. Particularly

the isomeric COFs with same chemical compositions provide an ideal platform to isolate and elucidate intrinsic topological effects in 2D COFs. Comprehensive characterizations reveal that the

sql

topology facilitates efficient charge separation and transfer

thereby enhancing photocatalytic performance. Moreover

without any sacrificial agents

ETBA-

sql

-COF exhibits a superior photocatalytic H

production rate up to 2042 μmol·g

–1

·h

–1

which is 1.57 times that of ETBA-

kgm

-COF (1303 μmol·g

–1

·h

–1

). This work provides an in-depth investigation into topology-property relationships in COFs and offers a rational strategy for the design and synthesis of high-performance photocatalysts.

关键词

Keywords

references

Siahrostami, S. H 2 O 2 electrosynthesis and emerging applications, challenges, and opportunities: a computational perspective. Chem Catal. 2023 , 3 , 100568..

Chen, Z.; Yao, D.; Chu, C.; Mao, S. Photocatalytic H 2 O 2 production systems: design strategies and environmental applications. Chem. Eng. J. 2023 , 451 , 138489..

[Zhao, K.; Chen, B.; Liang, L.; Chen, Y.; Yao, S.; Peng, Q.; Liu, Y.; Han, B. Microenvironment engineering of covalent organic frameworks for hydrogen peroxide synthesis via photocatalytic oxygen reduction. Chin. Chem. Lett . 2026 , 37 , 112032..

Sun, Y.; Han, L.; Strasser, P. A comparative perspective of electrochemical and photochemical approaches for catalytic H 2 O 2 production. Chem. Soc. Rev. 2020 , 49 , 6605−6631..

Zhao, E.; Xue, W.; Qin, S.; Guo, Y.; Xin, X.; Wang, H.; Zhang, Y.; Zuo, S. A review of H 2 O 2 electrosynthesis by 2-electron ORR and 2-electron WOR: From catalysts to electrochemical cells. Coord. Chem. Rev. 2025 , 545 , 217042..

Yong, Z.; Ma, T. Solar-to-H 2 O 2 catalyzed by covalent organic frameworks. Angew. Chem. Int. Ed. 2023 , 62 , e202308980..

Zeng, X.; Liu, Y.; Hu, X.; Zhang, X. Photoredox catalysis over semiconductors for light-driven hydrogen peroxide production. Green Chem. 2021 , 23 , 1466−1494..

Dong, W.; Qin, Z.; Liu, X.; Li, L. Nitrogen-doped engineering in covalent organic frameworks for photocatalytic synthesis of hydrogen peroxide. Chin. J. Chem. 2025 , 43 , 1504−1512..

Yu, K.; Gong, L.; Huang, Z.; Yu, Z.; Luo, F. Construction of three-component D-A-D isomer by a novel conversion strategy for largely boosting H 2 O 2 photosynthesis in open air and water. CCS Chem. 2025 , 7 , 2731−2741..

Chen, Z.; Weng, H.; Chu, C.; Yao, D.; Li, Q.; Zhang, C.; Mao, S. Nitrogen heterocyclic covalent organic frameworks for efficient H 2 O 2 photosynthesis and in situ water treatment. Nat. Commun. 2025 , 16 , 6943..

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

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..

Hu, X. L.; Li, H. G.; Tan, B. E. COFs-based porous materials for photocatalytic applications. Chinese J. Polym. Sci. 2020 , 38 , 673−684..

[Ding, L.; Pan, Z.; Wang, Q. 2D photocatalysts for hydrogen peroxide synthesis. Chin. Chem. Lett . 2024, 35 , 110125..

Cheng, J.; Wu, Y.; Zhang, W.; Wang, L.; Wu, X.; Xu, H. Unlocking topological effects in covalent organic frameworks for high-performance photosynthesis of hydrogen peroxide. Adv. Mater. 2025 , 37 , 2410247..

Xu, K.; Feng, Y.; Wen, F.; Xu, X.; Wang, H.; Shui, Q. J.; Huang, N. Topological control over porphyrin-based covalent organic frameworks for elucidating electron transfer characteristics. Angew. Chem. Int. Ed. 2025 , 64 , e202506977..

Yang, J.; Ghosh, S.; Roeser, J.; Acharjya, A.; Penschke, C.; Tsutsui, Y.; Rabeah, J.; Wang, T.; Djoko Tameu, S. Y.; Ye, M.-Y.; Grüneberg, J.; Li, S.; Li, C.; Schomäcker, R.; Van De Krol, R.; Seki, S.; Saalfrank, P.; Thomas, A. Constitutional isomerism of the linkages in donor–acceptor covalent organic frameworks and its impact on photocatalysis. Nat. Commun. 2022 , 13 , 6317..

Sun, H. H.; Zhou, Z. B.; Fu, Y.; Qi, Q. Y.; Wang, Z. X.; Xu, S.; Zhao, X. Azobenzene-bridged covalent organic frameworks boosting photocatalytic hydrogen peroxide production from alkaline water: one Atom Makes a Significant Improvement. Angew. Chem. Int. Ed. 2024 , 63 , e202409250..

Xu, Y.; Qiu, F.; Fu, Y.; Li, S. F.; Su, X.; Hong, K.; Zhang, M.-M.; Zhao, X.; Wang, Y.; Xu, S. Q. Solvent-driven precise control of stacking configurations in covalent organic frameworks for high-efficiency photocatalysis. Angew. Chem. Int. Ed. 2025 , 64 , e202512603..

[Liu, Z.; Liu, X.; Tang, L.; Pan, H.; Liu, X.; Jiang, J. Covalent organic frameworks-based heterojunctions for photocatalytic hydrogen peroxide production and in-situ application. Chin. Chem. Lett . 2025, 112024..

Krishnaraj, C.; Sekhar Jena, H.; Bourda, L.; Laemont, A.; Pachfule, P.; Roeser, J.; Chandran, C. V.; Borgmans, S.; Rogge, S. M. J.; Leus, K.; Stevens, C. V.; Martens, J.A.; Van Speybroeck, V.; Breynaert, E.; Thomas, A.; Van Der Voort, P. Strongly reducing (diarylamino)benzene-based covalent organic framework for metal-free visible light photocatalytic H 2 O 2 Generation. J. Am. Chem. Soc. 2020 , 142 , 20107−20116..

Yang, G. H.; Zhang, Z.; Yin, C. C.; Shi, X. S.; Wang, Y. Morphology engineering for covalent organic frameworks (COFs) by surfactant mediation and acid adjustment. Chinese J. Polym. Sci. 2022 , 40 , 338−344..

Ma, X.; Pan, H.; Gong, L.; Ding, X.; Zhou, X.; Liu, H.; Wang, R.; Qu, C.; Zhao, Y.; Qi, D.; Bian, Y.; Jiang, J. Electron/proton transport engineering in acylhydrazone-linked covalent organic framework for efficient solar-driven H 2 O 2 Production. Angew. Chem. Int. Ed. 2025 , 64 , e202511024..

Huang, P.; Peng, Y.-Y.; Wang, X. H.; Li, R. H.; Qin, M. H.; Zhang, M.; Wang, S. M.; Lu, M.; Li, S. L.; Lan, Y. Q. Charge-distribution and microenvironment dual regulation of covalent organic frameworks for enhancing photocatalytic H 2 O 2 and H 2 Production. Adv. Mater. 2026 , 38 , e07849..

Jin, E.; Geng, K.; Lee, K. H.; Jiang, W.; Li, J.; Jiang, Q.; Irle, S.; Jiang, D. Topology-templated synthesis of crystalline porous covalent organic frameworks. Angew. Chem. Int. Ed. 2020 , 59 , 12162−12169..

Yue, J.-Y.; Luo, J. X.; Pan, Z. X.; Zhang, R. Z.; Yang, P.; Xu, Q.; Tang, B. Regulating the topology of covalent organic frameworks for boosting overall H 2 O 2 photogeneration. Angew. Chem. Int. Ed. 2024 , 63 , e202405763..

Xiao, L. B.; Wu, Z. H.; Xin, J. J.; Cheng, Y. P.; Gui, B.; Sun, J. L.; Wang, C. A Fluorine-functionalized 3D covalent organic framework with entangled 2D layers. Chinese J. Polym. Sci. 2024 , 42 , 1210−1216..

Pang, Z. F.; Zhou, T. Y.; Liang, R. R.; Qi, Q. Y.; Zhao, X. Regulating the topology of 2D covalent organic frameworks by the rational introduction of substituents. Chem. Sci. 2017 , 8 , 3866−3870..

Huang, Q.; Gao, Q.; Wang, Y.; Wu, H.; Qian, C.; Liao, Y. Isomeric covalent organic frameworks: opportunities and challenges. Trends Chem. 2025 , 7 , 110 −123..

Liang, R. R.; Cui, F. Z.; A, R. H.; Qi, Q. Y.; Zhao, X. A Study on constitutional isomerism in covalent organic frameworks: controllable synthesis, transformation, and distinct difference in properties. CCS Chem. 2020 , 2 , 139−145..

Gui, B.; Xin, J.; Cheng, Y.; Zhang, Y.; Lin, G.; Chen, P.; Ma, J.-X.; Zhou, X.; Sun, J.; Wang, C. Crystallization of dimensional isomers in covalent organic frameworks. J. Am. Chem. Soc. 2023 , 145 , 11276−11281..

Zhou, T. Y.; Xu, S. Q.; Wen, Q.; Pang, Z. F.; Zhao, X. One-step construction of two different kinds of pores in a 2D covalent organic framework. J. Am. Chem. Soc. 2014 , 136 , 15885−15888..

Koppenol, W. H.; Stanbury, D. M.; Bounds, P. L. Electrode potentials of partially reduced oxygen species, from dioxygen to water. Free Radic. Biol. Med. 2010 , 49 , 317−322..

Nosaka, Y.; Nosaka, A. Y. Generation and detection of reactive oxygen species in photocatalysis. Chem. Rev. 2017 , 117 , 11302−11336..

Moon, G.-h.; Fujitsuka, M.; Kim, S.; Majima, T.; Wang, X.; Choi, W. Eco-friendly photochemical production of H 2 O 2 through O 2 reduction over carbon nitride frameworks incorporated with multiple heteroelements. ACS Catal. 2017 , 7 , 2886−2895..

Tan, H.; Zhou, P.; Liu, M.; Zhang, Q.; Liu, F.; Guo, H.; Zhou, Y.; Chen, Y.; Zeng, L.; Gu, L.; Zheng, Z.; Tong, M.; Guo, S. Photocatalysis of water into hydrogen peroxide over an atomic Ga-N 5 site. Nat. Synth. 2023 , 2 , 557−563..

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..

Yang, T.; Chen, Y.; Wang, Y.; Peng,X.; Kong, A. Weakly hydrophilic imine-linked covalent benzene–acetylene frameworks for photocatalytic H 2 O 2 production in the two-phase system. ACS Appl. Mater. Interfaces 2023 , 15 , 8066−8075..

Li, L.; Lv, X.; Xue, Y.; Shao, H.; Zheng, G.; Han, Q. Custom-design of strong electron/proton extractor on COFs for efficient photocatalytic H 2 O 2 production. Angew. Chem. Int. Ed. 2024 , 63 , e202320218..

Views

130

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Porous Organic Polymers for Photocatalytic Hydrogen Peroxide Production: Recent Advances and Future Perspectives

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

Sequence-encoded Conformation Pathways in Viscoelastic Microphase Separation of Multiblock Copolymers

Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF3 Incorporation

Related Author

Jia-Wei Xie

Bi-En Tan

Zhen-Yang Hu

Fu-Xiang Wen

Xiao-Yi Xu

Ning Huang

Ke-Jun Jin

Ying-Jian Yu

Related Institution

Huazhong University of Science and Technology

Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology

State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Polymer Science and Engineering, Zhejiang University

College of Physics Science and Technology, Kunming University

Engineering Research Center of High Performance Polymer and Molding Technology, Ministry of Education, College of Polymer Science and Engineering, Qingdao University of Science and Technology

⁰

Topologically Isomeric Effects on the Photocatalytic H2O2 Production Performance of Two-dimensional Covalent Organic Frameworks

DOI：10.1007/s10118-026-3602-0

摘要

Abstract

关键词

Keywords

references

Topologically Isomeric Effects on the Photocatalytic H₂O₂ Production Performance of Two-dimensional Covalent Organic Frameworks