Citation: Weixia Wang, Yongji Zhang, Fei Zhao, Libo Wang, Fanpeng Meng, Shuchao Qin, Jinsheng Zhao. Engineering π-delocalized network in fused-thiophene based polymers/g-C3N4 S-scheme heterojunctions for photocatalytic H2 evolution[J]. Chinese Journal of Structural Chemistry, ;2026, 45(3): 100833. doi: 10.1016/j.cjsc.2025.100833 shu

Engineering π-delocalized network in fused-thiophene based polymers/g-C3N4 S-scheme heterojunctions for photocatalytic H2 evolution

Carrier recombination in polymer photocatalysts involves both undissociated exciton decay and charge recombination, which are the main obstacles limiting their photocatalytic activity. Achieving efficient charge generation and separation in a polymer system is a fundamental strategy for the potential success of solar energy conversion to hydrogen, but it remains a huge challenge. In this study, we propose an innovative intermolecular π–π stacking strategy to construct a π-delocalized all-polymer S-scheme heterojunction for photocatalytic hydrogen evolution. Two conjugated porous polymers (CPPs)—PyB, composed of benzo[1,2-b:4,5-b′]dithiophene (BDT) and pyrene units, and PhB, composed of BDT and benzene—were synthesized and integrated with CN nanosheets. The highly planar and π-extended structure of PyB facilitated strong interfacial π–π stacking with CN, forming an extended π-delocalized network that enhanced the internal electric field (IEF), improved charge separation, and boosted visible-light absorption. As a result, the optimized PyB/CN-20 composite achieved a remarkable hydrogen evolution rate (HER) of 23.84 mmol⋅h−1⋅g−1 under visible light, approximately 287 times higher than that of pristine CN. This work underscores the critical role of polymer planarity and π-conjugation in heterojunction efficiency, and provides new insights into the rational design of π-delocalized S-scheme systems and establishes a general strategy for developing highly efficient, metal-free photocatalysts by leveraging molecular-level structural control.
- Conjugated porous polymers,
- Carbon nitride,
- S-scheme,
- Photocatalytic hydrogen evolution,
- Extended π-delocalized network
1. [1]
  Qiang Zhang , Weiran Gong , Huinan Che , Bin Liu , Yanhui Ao . S doping induces to promoted spatial separation of charge carriers on carbon nitride for efficiently photocatalytic degradation of atrazine. Chinese Journal of Structural Chemistry, 2023, 42(12): 100205-100205. doi: 10.1016/j.cjsc.2023.100205
2. [2]
  Yun Wang , Huage Lin , Jiaxiang Zong , Mengjiao Yu , Guangyu Wu , Weinan Xing . Interface design of S-scheme Co9S8/flower-like g-C3N4 van der Waals heterojunction with enhanced photocatalytic hydrogen production and tetracycline hydrochloride degradation. Chinese Journal of Structural Chemistry, 2026, 45(2): 100798-100798. doi: 10.1016/j.cjsc.2025.100798
3. [3]
  Fei Jin , Bolin Yang , Xuanpu Wang , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Facilitating efficient photocatalytic hydrogen evolution via enhanced carrier migration at MOF-on-MOF S-scheme heterojunction interfaces through a graphdiyne (CnH2n-2) electron transport layer. Chinese Journal of Structural Chemistry, 2023, 42(12): 100198-100198. doi: 10.1016/j.cjsc.2023.100198
4. [4]
  Kaihui Huang , Boning Feng , Xinghua Wen , Lei Hao , Difa Xu , Guijie Liang , Rongchen Shen , Xin Li . Effective photocatalytic hydrogen evolution by Ti3C2-modified CdS synergized with N-doped C-coated Cu2O in S-scheme heterojunctions. Chinese Journal of Structural Chemistry, 2023, 42(12): 100204-100204. doi: 10.1016/j.cjsc.2023.100204
5. [5]
  Linyu Zhu , Xu Tian , Guang Shi , Wenchi Zhang , Peisong Tang , Mohamed Bououdina , Sajjad Ali , Pengfei Xia . Assembling 3D cross-linked network by carbon nitride nanowires for visible-light photocatalytic H₂ evolution from dyestuffs wastewater. Chinese Chemical Letters, 2025, 36(12): 111088-. doi: 10.1016/j.cclet.2025.111088
6. [6]
  Yihu Ke , Shuai Wang , Fei Jin , Guangbo Liu , Zhiliang Jin , Noritatsu Tsubaki . Charge transfer optimization: Role of Cu-graphdiyne/NiCoMoO4 S-scheme heterojunction and Ohmic junction. Chinese Journal of Structural Chemistry, 2024, 43(12): 100458-100458. doi: 10.1016/j.cjsc.2024.100458
7. [7]
  Xiaoming Fu , Haibo Huang , Guogang Tang , Jingmin Zhang , Junyue Sheng , Hua Tang . Recent advances in g-C3N4-based direct Z-scheme photocatalysts for environmental and energy applications. Chinese Journal of Structural Chemistry, 2024, 43(2): 100214-100214. doi: 10.1016/j.cjsc.2024.100214
8. [8]
  Qiang Yu , Shuhan Sun , Xianming Jin , Ruiqiang Yan , Bingjing He , Nikolay Sirotkin , Alexander Agafonov , Xianqiang Xiong , Kangle Lv . Type-I heterojunction photocatalysis: Enhanced activity via ZnIn2S4/MnCo2O4.5 interfacial electric fields. Chinese Journal of Structural Chemistry, 2025, 44(7): 100620-100620. doi: 10.1016/j.cjsc.2025.100620
9. [9]
  Zheng Liu , Yuqing Bian , Graham Dawson , Jiawei Zhu , Kai Dai . Rational constructing of Zn_0.5Cd_0.5S-diethylenetriamine/g-C₃N₄ S-scheme heterojunction with enhanced photocatalytic H₂O₂ production. Chinese Chemical Letters, 2025, 36(9): 111272-. doi: 10.1016/j.cclet.2025.111272
10. [10]
  Xinxin Liang , Yongqian Cui , Qingyun Tian , Tingting Jia , Qibing Dong , Ximing Li , Ting Gao , Chao Ma , Chuanyi Wang . Photoreforming polylactic acid plastics into pyruvate over CdS/Bi₄Ti₃O₁₂ S-scheme heterojunction: Successive removal of hydrogen from α-C. Chinese Chemical Letters, 2026, 37(2): 111097-. doi: 10.1016/j.cclet.2025.111097
11. [11]
  Ziruo Zhou , Wenyu Guo , Tingyu Yang , Dandan Zheng , Yuanxing Fang , Xiahui Lin , Yidong Hou , Guigang Zhang , Sibo Wang . Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100245-100245. doi: 10.1016/j.cjsc.2024.100245
12. [12]
  Yueting Ma , Zhiyan Feng , Yuxin Dong , Zhiyong Yan , Hou Wang , Yan Wu . Harnessing the interfacial sulfur-edge and metal-edge sites in ZnIn₂S₄/MnS heterojunctions boosts charge transfer for photocatalytic hydrogen production. Chinese Chemical Letters, 2025, 36(6): 110922-. doi: 10.1016/j.cclet.2025.110922
13. [13]
  Linping Li , Junhui Su , Yanping Qiu , Yangqin Gao , Ning Li , Lei Ge . Design and fabrication of ternary Au/Co3O4/ZnCdS spherical composite photocatalyst for facilitating efficient photocatalytic hydrogen production. Chinese Journal of Structural Chemistry, 2024, 43(12): 100472-100472. doi: 10.1016/j.cjsc.2024.100472
14. [14]
  Haiyan Yin , Abdusalam Ablez , Zhuangzhuang Wang , Weian Li , Yanqi Wang , Qianqian Hu , Xiaoying Huang . Novel open-framework chalcogenide photocatalysts: Cobalt cocatalyst valence state modulating critical charge transfer pathways towards high-efficiency hydrogen evolution. Chinese Journal of Structural Chemistry, 2025, 44(4): 100560-100560. doi: 10.1016/j.cjsc.2025.100560
15. [15]
  Hongrui Zhang , Miaoying Cui , Yongjie Lv , Yongfang Rao , Yu Huang . A short review on research progress of ZnIn₂S₄-based S-scheme heterojunction: Improvement strategies. Chinese Chemical Letters, 2025, 36(4): 110108-. doi: 10.1016/j.cclet.2024.110108
16. [16]
  Futao Yi , Ying Liu , Yao Chen , Jiahao Zhu , Quanguo He , Chun Yang , Dongge Ma , Jun Liu . Dual S-Scheme g-C₃N₄/Ag₃PO₄/g-C₃N₅ photocatalysts for removal of tetracycline pollutants through enhanced molecular oxygen activation. Chinese Chemical Letters, 2025, 36(8): 110544-. doi: 10.1016/j.cclet.2024.110544
17. [17]
  Xiuzheng Deng , Changhai Liu , Xiaotong Yan , Jingshan Fan , Qian Liang , Zhongyu Li . Carbon dots anchored NiAl-LDH@In₂O₃ hierarchical nanotubes for promoting selective CO₂ photoreduction into CH₄. Chinese Chemical Letters, 2024, 35(6): 108942-. doi: 10.1016/j.cclet.2023.108942
18. [18]
  Tao Zhou , Xu Han , Wangwang Shen , Fang Ji , Menglong Liu , Yingyu Song , Wen-Wen He . Construction of NiS/CTF heterojunction photocatalyst with an outstanding photocatalytic hydrogen evolution performance. Chinese Chemical Letters, 2025, 36(11): 110415-. doi: 10.1016/j.cclet.2024.110415
19. [19]
  Yue Pan , Wenping Si , Yahao Li , Haotian Tan , Ji Liang , Feng Hou . Promoting exciton dissociation by metal ion modification in polymeric carbon nitride for photocatalysis. Chinese Chemical Letters, 2024, 35(12): 109877-. doi: 10.1016/j.cclet.2024.109877
20. [20]
  Yan-Ling Li , Yue Xu , Chen-Hong Wang , Rui Wang , Shuang-Quan Zang . Dye-stabilized atomically precise copper clusters for enhanced photocatalytic hydrogen evolution. Chinese Chemical Letters, 2025, 36(10): 111256-. doi: 10.1016/j.cclet.2025.111256

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沈阳化工大学材料科学与工程学院沈阳 110142