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DOI: https://doi.org/10.6023/A25030077

研究论文

基于sp2-碳连接具有D-A结构共价有机框架的构筑及其光催化产双氧水性能研究

  • 闫生荣 ,
  • 刘文浩 ,
  • 段芳 ,
  • 陈明清 ,
  • 东为富 ,
  • 陆双龙 ,
  • 杜明亮
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  • a江南大学化学与材料工程学院 合成与生物胶体教育部重点实验室 无锡 214122;
    b南通科技职业学院环境与生物工程学院 江苏省环境功能材料与污染治理工程技术研究开发中心 南通 226007
* E-mail: duanfang@jiangnan.edu.cn; mqchen@jiangnan.edu.cn.

收稿日期: 2025-03-12

  网络出版日期: 2025-06-03

基金资助

项目受国家重点研发计划(No. 2023YFF1105200)、国家自然科学基金(No. 52173201)、江苏省研究生科研与实践创新计划项目(No. KYCX18_1808)和江苏省高职院校教师专业带头人高端研修项目(No. 2023GRFX045)资助.

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Constructing of sp2-Carbon Linked Covalent Organic Frameworks with D-A Structure and Evaluating Their Photocatalytic Performance towards Hydrogen Peroxide Production

  • Yan Shengrong ,
  • Liu Wenhao ,
  • Duan Fang ,
  • Chen Mingqing ,
  • Dong Weifu ,
  • Lu Shuanglong ,
  • Du Mingliang
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  • aSchool of Chemical and Material Engineering, Jiangnan University, Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, Wuxi 214122, China;
    bSchool of Environmental and Biological Engineering, Nantong College of Science and Technology, Jiangsu Engineering Research Center of Environmental Functional Materials and Pollution Control, Nantong 226007, China

Received date: 2025-03-12

  Online published: 2025-06-03

Supported by

National Key Research and Development Program of China (No. 2023YFF1105200), the National Natural Science Foundation of China (No. 52173201), Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX18_1808), and High-end Training Program for Teachers' Professional Leaders in Higher Vocational Colleges of Jiangsu Province in 2023 (No. 2023GRFX045).

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摘要

设计高度共轭和电子给体-受体(D-A)结构是提升共价有机框架(COFs)电荷分离和转移的有效手段. 鉴于此,通过Knoevenagel缩合反应构筑了两种sp²-碳连接的BBpy-COF和BBph-COF光催化剂,并系统研究了其光催化产双氧水(H2O2)性能. 实验结果表明,BBpy-COF光催化H2O2生成速率可达1394.7 µmol·g-1·h-1,为BBph-COF (656.5 µmol·g-1·h-1)的2.12倍,其性能提升归因于苯并三噻吩(Btt)电子给体与联吡啶(Bpy)电子受体间的强D-A作用和C=C双键连接的共轭增强效应调控优化了光生载流子的分离效率,最后依靠氧还原反应(ORR)活性位点Bpy,高效通过两步单电子ORR路径实现光催化产H2O2. 本项工作为合理设计和构筑高效COFs光催化材料提供了一定的参考.

关键词： sp2-碳连接; D-A结构; 共价有机框架; 光催化产双氧水

本文引用格式

闫生荣 , 刘文浩 , 段芳 , 陈明清 , 东为富 , 陆双龙 , 杜明亮 . 基于sp2-碳连接具有D-A结构共价有机框架的构筑及其光催化产双氧水性能研究[J]. 化学学报, 0 : 25030077 -25030077 . DOI: 10.6023/A25030077

Abstract

Covalent organic frameworks (COFs) are crystalline organic materials connected by covalent bonds. Due to their pre-designed structures similar to the modular assembly of Lego bricks, adjustable optical and electronic properties, high chemical and thermal stability and so on, COFs have been proved to be promising photocatalysts for the production of hydrogen peroxide (H2O2). However, similar to other photocatalysts, COFs also suffer from the common challenge of inefficient separation of photogenerated charge carriers. Constructing COFs with high conjugation and electron donor-acceptor (D-A) structure is an effective strategy to improve the separation and transfer capacity of photogenerated charges. Herein, through a simple yet effective one-step solvothermal synthesis approach, two kinds of sp2-carbon conjugated COFs with D-A structure (designated as BBpy-COF and BBph-COF) were successfully fabricated by the Knoevenagel condensation reaction, and their photocatalytic performance towards H2O2 production was evaluated. BBpy-COF with the linker of 2,2'-([2,2'-bipyridine]-5,5'-diyl) diacetonitrile (Bpy-2CN) displayed a high photocatalytic H2O2 production rate of 1394.7 µmol g-1 h-1, with 2.12-fold enhancement compared to BBph-COF with the linker of 4,4'-biphenyldiacetonitrile (Bph-2CN). Through a series of experiments such as the electron paramagnetic resonance (EPR) spectroscopy and rotating disk electrode (RDE) measurements as well as density functional theory (DFT) calculations, the photocatalytic mechanism was revealed that compared with BBph-COF, by virtue of the D-A structure constructed by the strong electron donor benzo [1,2-b:3,4-b':5,6-b''] trithiophene-2,5,8-tricarbaldehyde (Btt) with the strong electron acceptor bipyridine (Bpy) and the C=C double bond connection to enhance the conjugation of the framework, BBpy-COF possessed a stronger electron push-pull effect to enhance the visible-light absorption capacity and accelerate the separation and migration of photogenerated e--h+ pairs. Ultimately, leveraging Bpy as active sites of oxygen reduction reaction (ORR), BBpy-COF achieved efficient photocatalytic H2O2 production via a two-step single-electron ORR pathway. This work employs an innovative ‘triple-in-one’ integration strategy that combines D-A structure construction, the C=C double bond linkages and embedding Bpy as ORR active sites into the skeleton of COFs, offering valuable insights and references for the rational design and fabrication of high-performance COFs-based photocatalytic materials.

Key words： sp2-carbon linkage; D-A structure; covalent organic frameworks; photocatalytic hydrogen peroxide production

参考文献

[1] Yu X.; Huang W.; Li, Y. Acta Chim. Sinica2022, 80, 1494(in Chinese).
(于潇涵, 黄伟, 李彦光, 化学学报, 2022, 80, 1494.)
[2] Wang D.; Feng B.; Zhang X.; Liu Y.; Pei Y.; Qiao M.; Zong, B. Acta Chim. Sinica2022, 80, 772(in Chinese).
(王丹, 封波, 张晓昕, 刘亚楠, 裴燕, 乔明华, 宗保宁, 化学学报, 2022, 80, 772.)
[3] Dong W.; Qin Z.; Liu X.; Li, L. Chin. J. Chem.2025, 43, 1504.
[4] Chi W.; Liu B.; Dong Y.; Zhang J.; Sun X.; Pan C.; Zhao H.; Ling Y.; Zhu, Y. Appl. Catal. B Environ. Energy.2024, 355, 124077.
[5] Kou J.; Wang G.; Guo H.; Li L.; Fang J.; Ma J.; Dong, Z. Appl. Catal. B Environ. Energy.2024, 352,124020.
[6] Wang H.; Yang C.; Chen F.; Zheng G.; Han, Q. Angew. Chem. Int. Ed.2022, 61, e202202328.
[7] Zhang F.; Wang Y.; Zhao Q.; Zhao H.; Dong X.; Gu X.; Sheng H.; Sarina S.; Lang X. ACS Appl. Mater. Interfaces.2025, 17,1097.
[8] Zou L.; Sa R.; Zhong H.; Lv H.; Wang X.; Wang R. ACS Catal.2022, 12, 3550.
[9] Sun H.-H.; Zhou Z.-B.; Fu Y.; Qi Q.-Y.; Wang Z.-X.; Xu S.; Zhao, X. Angew. Chem. Int. Ed.2024, 63, e202409250.
[10] Xiao J.-Z.; Zhao Z.-H.; Zhang N.-N.; Che H.-T.; Qiao X.; Zhang G.-Y.; Chu X.; Wang Y.; Dong H.; Zhang F.-M. Chin. J. Catal.2025, 44, 219.
[11] Mou Y.; Wu X.; Qin C.; Chen J.; Zhao Y.; Jiang L.; Zhang C.; Yuan X.; Ang E. H.; Wang, H. Angew. Chem. Int. Ed.2023, 62, e202309480.
[12] Seo J.-M.; Noh H.-J.; Jeong H. Y.; Baek J.-B. J. Am. Chem. Soc.2019, 141, 11786.
[13] Qian Y.; Han Y.; Zhang X.; Yang G.; Zhang G.; Jiang H.-L. Nat. Commun.2023, 14, 3083.
[14] Kandambeth S.; Shinde D. B.; Panda M. K.; Lukose B.; Heine T.; Banerjee, R. Angew. Chem. Int. Ed.2013, 52, 13052.
[15] Halder A.; Karak S.; Addicoat M.; Bera S.; Chakraborty A.; Kunjattu S. H.; Pachfule P.; Heine T.; Banerjee, R. Angew. Chem. Int. Ed.2018, 57,5797.
[16] Ascherl L.; Sick T.; Margraf J. T.; Lapidus S. H.; Calik M.; Hettstedt C.; Karaghiosoff K.; Döblinger M.; Clark T.; Chapman K. W.; Auras F.; Bein T. Nat. Chem.2016, 8, 310.
[17] Xu H.; Gao J.; Jiang D. Nat. Chem.2015, 7, 905.
[18] Chen R.; Shi J.-L.; Ma Y.; Lin G.; Lang X.; Wang, C. Angew. Chem. Int. Ed.2019, 58, 6430.
[19] Li S.; Xu S.; Lin E.; Wang T.; Yang H.; Han J.; Zhao Y.; Xue Q.; Samorì P.; Zhang Z.; Zhang T. Nat. Chem.2025, 17, 226.
[20] Liao Q.; Sun Q.; Xu H.; Wang Y.; Xu Y.; Li Z.; Hu J.; Wang D.; Li H.; Xi, K. Angew. Chem. Int. Ed.2023, 62, e202310556.
[21] Liu J.-C.; Tuo C.; Xiao W.-Y.; Qi M.-Y.; Yusran Y.; Wang Z.-T.; Li H.; Guo C.-S.; Song J.-L.; Qiu S.-L.; Xu Y.-J.; Fang, Q. Angew. Chem. Int. Ed.2025, 64, e202416240.
[22] Liu W.; Zhang Y.; Wang J.; Shang X.; Zhang C.; Wang, Q. Coord. Chem. Rev.2024, 516, 215997.
[23] Liu W.; Li Y.; Duan F.; Liu H.; Ren Y.; Yan S.; Lu S.; Du M.; Chen X.; Wang, J. J. Mater. Chem. A.2025, 13, 786.
[24] Gu Y.-Y.; Wang J.; Tang Q.; Wei H.; Ning J.; Lan X.; Wang X.; Li X.; Jia Y.; Wang S.; Hao L. ACS Catal.2024, 14,11262.
[25] Dai L.; Dong A.; Meng X.; Liu H.; Li Y.; Li P.; Wang, B. Angew. Chem. Int. Ed.2023, 62, e202300224.
[26] Xu M.; Yu S.; Li W.; Li C.; Peng Y.; Yu F. Polym. Chem.2023, 14, 5133.
[27] Wei H.; Ning J.; Cao X.; Li X.; Hao, L. J. Am. Chem. Soc.2018, 140, 11618.
[28] Gu C.-C.; Ni C.-Q.; Wu R.-J.; Deng L.; Zou J.; Li H.; Tong C.-Y.; Xu F.-H.; Wang B.-C.; Zhu, R.-L. J. Colloid Interface Sci.2024, 658, 450.
[29] Li Z.; Deng T.; Ma S.; Zhang Z.; Wu G.; Wang J.; Li Q.; Xia H.; Yang S.-W.; Liu, X. J. Am. Chem. Soc.2023, 145, 8364.
[30] Li J.; Jia J.; Suo J.; Li C.; Wang Z.; Li H.; Valtchev V.; Qiu. S.; Liu X.; Fang, Q. J. Mater. Chem. A.2023, 11,18349.
[31] Qin C.; Wu X.; Tang L.; Chen X.; Li M.; Mou Y.; Su B.; Wang S.; Feng C.; Liu J.; Yuan X.; Zhao Y.; Wang H. Nat. Commun.2023, 14, 5238.
[32] Liu J.; Zhang W.; Shen J.; Feng L.; Yao Y.; Peng Q.Angew. Chem. Int. Ed. 2025, e202424720.
[33] Ji R.; Dong Y.; Sun X.; Pan C.; Yang Y.; Zhao H.; Zhu, Y. Appl. Catal. B Environ. Energy.2024, 349, 123884.
[34] Huang F.; Wang Y.; Dong X.; Lang, X. J. Mater. Chem. A.2024, 12, 7036.
[35] Yue J.-Y.; Song L.-P.; Fan Y.-F.; Pan Z.-X.; Yang P.; Ma Y.; Xu Q.; Tang, B. Angew. Chem. Int. Ed.2023, 62, e202309624.
[36] Jin X.; Lv C.; Zhou X.; Ye L.; Xie H.; Liu Y.; Su H.; Zhang B.; Chen G. ChemSusChem.2019, 12, 2740.
[37] Shiraishi Y.; Takii T.; Hagi T.; Mori S.; Kofuji Y.; Kitagawa Y.; Tanaka S.; Ichikawa S.; Hirai T.Nat. Mater. 2019, 18, 985.
[38] Du J.; Feng S.; Zhang J.; Zhang Y.; Wang S.; Han L.; Chen, J. Chin. J. Org. Chem.2022, 42, 2967(in Chinese).
(杜俊平, 封珊珊, 张婕, 张永辉, 王诗文, 韩莉峰, 陈俊利, 有机化学, 2022, 42, 2967.)
[39] Liu X.; Li H.; Xu N.; Guo Y.; Zhang X.; Wang, X. Chin. J. Chem.2024, 42, 2970.
[40] Xiang Y.; Xia Z.; Hu W.; Tong C.; Xiao Y.; Lü, C. Chin. J. Chem. 2024, 42, 1975.
[41] Yan S.; Zhang L.; Shi S.; Ren Y.; Liu W.; Li Y.; Duan F.; Lu S.; Du M.; Chen, M. Chem. Res. Chinese Universities.2025, 41, 121.
[42] Zhang H.; Wei W.; Chi K.; Zheng Y.; Kong X. Y.; Ye L.; Zhao Y.; Zhang, K. A. L. ACS Catal.2024, 14, 17654.
[43] Liu Y.; Han W.-K.; Chi W.; Mao Y.; Jiang Y.; Yan X.; Gu, Z.-G. Appl. Catal. B Environ.2023, 331, 122691.
[44] Liu J.; Li C.; Liu Y.; Wang Y.; Fang, Q. Acta Chim. Sinica2023, 81, 884(in Chinese).
(刘建川, 李翠艳, 刘耀祖, 王钰杰, 方千荣, 化学学报, 2023, 81, 884.)
[45] Luo X.; Zhou S.; Zhou S.; Wang D.; Zhang Y.; Hao X.; Liu G.; Jin L.; Liu P.; Gu, P. Sep. Purif. Technol.2025, 355, 129774.
[46] Pan C.; Bian G.; Zhang Y.; Lou Y.; Zhang Y.; Dong Y.; Xu J.; Zhu, Y. Appl. Catal. B Environ.2022, 316, 121675.
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