单原子取代调控三（4-乙炔苯）胺类共轭孔聚合物的光催化水分解析氢性能

doi:10.6023/cjoc202603040

单原子取代调控三（4-乙炔苯）胺类共轭孔聚合物的光催化水分解析氢性能

杜俊平^*, 井森彪, 张鲜放, 韩莉锋, 张捷, 王诗文, 陈俊利, 绪连彩^*

河南省环己醇催化分离工程研究中心郑州轻工业大学材料与化学工程学院,郑州 450002

收稿日期:2026-03-30 修回日期:2026-05-18
基金资助:
国家自然科学基金(No.21805248,U2004196)、河南省自然科学基金(No.162300410318)、中国科学院上海有机化学研究所开放项目(No.K2016-8)和郑州轻工业学院博士基金(No.2013BSJJ017)资助项目.

Efficient modulation of Photocatalytic Water Splitting Hydrogen Evolution Performance for Tris(4-ethynylphenyl)amine-Based Conjugated porous Polymers via Single-Atom Substitution

Junping Du^*, Senbiao Jing, Xianfang Zhang, Lifeng Han, Jie Zhang, Shiwen Wang, Junli Chen, Liancai Xu^*

Henan Cyclohexanol Catalytic Separation Engineering Research Center Department of materials and chemical engineering Zhengzhou University of Light Industry, Zhengzhou, 450002

Received:2026-03-30 Revised:2026-05-18
Contact: ^*E-mail: dujunping@zzuli.edu.cn
Supported by:
National Natural Science Foundation of China (No.21805248, U2004196), the Natural Science Foundation of Henan Province (No.162300410318), the Open Project of Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (No.K2016-8) and the Doctor Research Project of Zhengzhou University of Light Industry (No.2013BSJJ017).

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摘要/Abstract

光催化水分解制氢是实现太阳能高效转化利用、缓解目前环境与能源危机的理想途径之一。新型、高性能且具备应用潜力的光催化剂,是推动该技术走向实用化的关键。分别以2,7-二溴-9-芴酮及其9-位被单原子硫取代的结构类似物3,7-二溴-5,5-二氧-二苯并噻吩作为共聚双官能团单体,运用Sonogashira-Hagihara偶联反应,制备得到两种三(4-乙炔苯)胺（TEA）类共轭孔聚合物TEA-FON和TEA-DTS。研究结果表明两种聚合物均表现出优异的溶剂稳定性、化学稳定性和热稳定性,同时具备较高的比表面积;无助催化剂存在下,均展现出良好的光催化水分解制氢活性。相同反应及测试条件下,TEA-FON的光催化析氢效率是TEA-DTS的1.5倍。深入研究证实,析氢效率差异源于共聚单体的单原子取代效应,该取代效应有效调控了聚合物的光吸收性能、光生载流子分离能力及电荷迁移速率。该研究证实通过共聚单体单原子取代效应能够实现TEA类共轭孔聚合物的高效调控。

关键词: 单原子取代, 三（4-乙炔苯）胺, 共轭孔聚合物, 光催化, 析氢

Photocatalytic water splitting hydrogen evolution has been widely recognized as one of the most promising strategies for the exploitation and utilization of solar energy, thereby alleviating the pressing environmental and energy crises. To realize this technology, one of the key factors is the development of novel, high-performance, and practically applicable photocatalysts. Herein, two tris(4-ethynylphenyl)amine (TEA)-based conjugated porous polymers (CPPs) TEA-FON and TEA-DTS have been synthesized via the Sonogashira-Hagihara coupling reaction with 2,7-dibromo-9-fluorenone and its structural analog 3,7-dibromo-5,5-dioxidodibenzothiophene which has been substituted at 9-position with single-atom sulfur as the difunctional comonomers, respectively. It has been demonstrated that both polymers possess excellent solvent, chemical, and thermal stabilities, along with a large specific surface area. More importantly, they exhibit remarkable photocatalytic hydrogen evolution activity even without the assistance of any cocatalysts. Notably, under identical reaction conditions, the hydrogen evolution rate (HER) of TEA-FON is 1.5 times higher than that of TEA-DTS. Further systematic investigations have revealed that the discrepancy in HER originates from the single-atom substitution, which efficiently modulates the light-harvesting efficiency, photogenerated carrier separation efficiency, and charge transfer rate of the polymers. It has suggested that photocatalytic performance of TEA-based CPPs can been modulated efficiently with the regulation of single-atom substitution of comonomers.

Key words: single-atom substitution, tris(4-ethynylphenyl)amine, conjugated porous polymer, photocatalytic, hydrogen evolution

引用此文

杜俊平, 井森彪, 张鲜放, 韩莉锋, 张捷, 王诗文, 陈俊利, 绪连彩. 单原子取代调控三（4-乙炔苯）胺类共轭孔聚合物的光催化水分解析氢性能[J]. 有机化学, doi: 10.6023/cjoc202603040.

Junping Du, Senbiao Jing, Xianfang Zhang, Lifeng Han, Jie Zhang, Shiwen Wang, Junli Chen, Liancai Xu. Efficient modulation of Photocatalytic Water Splitting Hydrogen Evolution Performance for Tris(4-ethynylphenyl)amine-Based Conjugated porous Polymers via Single-Atom Substitution[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202603040.

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参考文献

[1] Hisatomi T.; Yamada T.; Nishiyama H.; Takata T.; Domen, K. Nat. Rev. Mater.2025, 10, 769.
[2] Kumar S.; Kumar A.; Kumar A.; Krishnan V. Catal. Rev.2019, 62, 346.
[3] Lee G.-J.; Anandan S.; Masten S. J.; Wu, J. J. Renew. Energy2016, 89, 18.
[4] Maeda K.; Teramura K.; Lu D.; Takata T.; Saito N.; Inoue Y.; Domen K. Nature2006, 440, 295.
[5] Rahman M.; Tian H.; Edvinsson, T. Angew. Chem. Int. Ed.2020, 59, 16278.
[6] Rajaambal S.; Sivaranjani K.; Gopinath, C. S. J. Chem. Sci.2015, 127, 33.
[7] Shu C.; Han C.; Yang X.; Zhang C.; Chen Y.; Ren S.; Wang F.; Huang F.; Jiang, J. X. Adv. Mater.2021, 33, 2008498.
[8] Takata T.; Jiang J.; Sakata Y.; Nakabayashi M.; Shibata N.; Nandal V.; Seki K.; Hisatomi T.; Domen K. Nature2020, 581, 411.
[9] Yu F.; Wang L.; Xing Q.; Wang D.; Jiang X.; Li G.; Zheng A.; Ai F.; Zou, J.-P. Chin. Chem. Lett.2020, 31, 1648.
[10] Zhao Q.; Ji M.; Qian H.; Dai B.; Weng L.; Gui J.; Zhang J.; Ouyang M.; Zhu H. Adv. Mater.2013, 26, 1387.
[11] Zhou P.; Navid I. A.; Ma Y.; Xiao Y.; Wang P.; Ye Z.; Zhou B.; Sun K.; Mi Z. Nature2023, 613, 66.
[12] Tian C.; Liu X.; Yu M.; Wu Y.; Che Y.; Zhang W.; Zhu, W. J. Funct. Poly.2025, 38, 216 (in chinese)
(田昌昊, 刘雪岩, 虞苗杰, 吴永真, 车瑜, 张维伟, 朱为宏. 功能高分子学报, 2025, 38, 216.)
[13] Dubey N.; Labhsetwar N.; Devotta S.; Rayalu S.Catal. Today 2007, 129, 428.
[14] Guo L.; Niu Y.; Xu H.; Li Q.; Razzaque S.; Huang Q.; Jin S.; Tan, B. J. Mater. Chem. A.2018, 6, 19775.
[15] Pan Z.; Hisatomi T.; Wang Q.; Nakabayashi M.; Shibata N.; Pan C.; Takata T.; Domen, K. Appl. Catal. A: Gen.2016, 521, 26.
[16] Nishioka S.; Osterloh F. E.; Wang X.; Mallouk T. E.; Maeda, K. Nat. Rev. Method. Prime.2023, 3, 42.
[17] Dong Y.; Zhang X.; Yue H.; Wang L.; Zhao J.; Zhao F.; Wei Z.; Zhang, J. J. Colloid. Interf. Sci.2026, 709, 139896.
[18] Li Y.; Tsang, S. C. E. Mater. Today. Sustain.2020, 9, 100032.
[19] Jafari T.; Moharreri E.; Amin A.; Miao R.; Song W.; Suib S. Molecules2016, 21, 900.
[20] Li R.; Luan J.; Zhang Y.; Jiang L.; Yan H.; Chi Q.; Yan, Z. Renew. Sust. Energ. Rev.2024, 206, 114863.
[21] Liu P.; Ye F.; Han C.; Gao C.; Yang H.; Chen X.; Huang, Y. Chem. Eng. J.2026, 531, 174169.
[22] Yi D.; Li, Y. Acta Phys.-Chim. Sin.2026, 42, 100220 (in chinese)
(易丹凤,李玉麟,物理化学学报, 2026, 42, 100220).
[23] Zhang Y.; Heo Y.-J.; Lee J.-W.; Lee J.-H.; Bajgai J.; Lee K.-J.; Park S.-J. Catal.2018, 8, 655.
[24] Chen S.; Vequizo J. J.M.; Hisatomi, T.; Nakabayashi, M.; Lin, L.; Wang, Z.; Yamakata, A.; Shibata, N.; Takata, T.; Yamada, T.; Domen, K.
Chem. Sci.2020, 11, 6436.
[25] Dai S.; Montero-Lanzuela E.; Tissot A.; Baldoví H. G.; García H.; Navalón S.; Serre C. Chem. Sci.2023, 14, 3451.
[26] Yang Y.; Liu E.; Dai H.; Kang L.; Wu H.; Fan J.; Hu X.; Liu, H. Int. J. Hydrogen Energ.2014, 39, 7664.
[27] Anwar S.; Aslam Z.; Aslam U.; Mehmood U.; Rana A. G.; Mahmood N.; Rafique A.Fuel 2026, 404, 136280.
[28] Zhang G.; Lan Z. A.; Wang, X. Angew. Chem. Int. Ed.2016, 55, 15712.
[29] Maeda K.; Domen, K. J. Phys. Chem. Lett.2010, 1, 2655.
[30] Cheng J.-Z.; Tan Z.-R.; Xing Y.-Q.; Shen Z.-Q.; Zhang Y.-J.; Liu L.-L.; Yang K.; Chen L.; Liu, S.-Y. J. Mater. Chem. A.2021, 9, 5787.
[31] Cooper A. I.Adv. Mater. 2009, 21, 1291.
[32] Wong Y. L.; Tobin J. M.; Xu Z.; Vilela, F. J. Mater. Chem. A.2016, 4, 18677.
[33] Yu J.; Sun X.; Xu X.; Zhang C.; He, X. Appl. Catal. B: Environ.2019, 257, 117935.
[34] Albano G.; Aronica L. A.; Biver T.; Detti R.; Pucci A.ChemistrySelect 2018, 3, 1749.
[35] Barman S.; Singh A.; Rahimi F. A.; Maji, T. K. J. Am. Chem. Soc.2021, 143, 16284.
[36] Cui L.; Yu S.; Gao W.; Zhang X.; Deng S.; Zhang, C.-Y. ACS Appl. Mater. Interfaces2020, 12, 7966.
[37] Dai C.; Zhong L.; Gong X.; Zeng L.; Xue C.; Li S.; Liu B.Green. Chem. 2019, 21, 6606.
[38] Guo B.; Liu Q.; Su Q.; Liu W.; Ju P.; Li G.; Wu, Q. J. Mater. Sci.2018, 53, 15746.
[39] Ren S.; Dawson R.; Laybourn A.; Jiang J.-x.; Khimyak Y.; Adams D. J.; Cooper, A. I. Polym. Chem.2012, 3, 928.
[40] Xu J.; Zhang C.; Qiu Z.; Lei Z.; Chen B.; Jiang J. X.; Wang, F. Macromol. Chem. Phys.2017, 218, 1700275.
[41] Ren Q.; Li X.; Li M.; Ruan J.; Dong S.; Li N.; Xu Q.; Li H.; Chen D.; Lu, J. Adv. Funct. Mater.2025, 36, e21077.
[42] Liu W.; Zhu Z.; Liu X.; Zhao M.; Jiao R.; Mu P.; Sun H.; Li, A. Chem. Eng. J.2026, 534, 175099.
[43] 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).
[44] Jiang J-X.; Su F.; Trewin A.; Wood C. D.; Niu H.; Jones J. T. A.; Khimyak Y. Z.; Cooper, A. I. J. Am. Chem. Soc.2008, 130, 7710.
[45] Du J.; Zhang X.; Zhou K.; Liang X.; Xu L.; Wang S.; Chen, J. J. Appl. Polym. Sci.2025, 142, e56776.