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

doi:10.6023/cjoc202603040

Chinese Journal of Organic Chemistry Previous Articles Next Articles

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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Abstract

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

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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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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

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

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