Citation: Ruixiang Wang, Jiajie Hou, Jinze He, Junyao Huang, Li Zhao, Ravi Naidu, Dionissios Mantzavinos, Grigorios Beligiannis, Nikolaos Andritsos, Fei Shen, Yongjia Lei. Surface hydroxylation engineering of pyrene-based COFs to promote oxygen activation for visible-light-catalyzed degradation of antibiotics[J]. Chinese Chemical Letters, ;2026, 37(6): 112143. doi: 10.1016/j.cclet.2025.112143 shu

Surface hydroxylation engineering of pyrene-based COFs to promote oxygen activation for visible-light-catalyzed degradation of antibiotics

Ruixiang Wang ^{a, b} ,
Jiajie Hou ^a ,
Jinze He ^a ,
Junyao Huang ^a ,
Li Zhao ^{a, b} ,
Ravi Naidu ^c ,
Dionissios Mantzavinos ^d ,
Grigorios Beligiannis ^e ,
Nikolaos Andritsos ^e ,
Fei Shen ^{a, b, *,} ,
Yongjia Lei ^{a, b, *,}

a.
College of Environmental Sciences, Sichuan Agricultural University, Chengdu 611130, China
b.
Sichuan Provincial Engineering Research Center of Agricultural Non-point Source Pollution Control, Sichuan Agricultural University, Chengdu 611130, China
c.
Global Centre for Environmental Remediation (GCER), University of Newcastle, Callaghan, NSW 2308, Australia
d.
Department of Chemical Engineering, University of Patras, Caratheodory 1, University Campus, GR-26504 Patras, Greece
e.
School of Agricultural Sciences, University of Patras, Agrinio 30100, Greece

fishen@sicau.edu.cn

yongjia.lei@sicau.edu.cn

Received Date: 7 May 2025
Revised Date: 19 September 2025
Accepted Date: 20 November 2025
Available Online: 21 November 2025

Figures(5)

Covalent organic frameworks (COFs) with structural designability and functional predictability display great potential as emerging metal-free semiconductor catalysts in the field of photocatalytic degradation for antibiotics. However, the disadvantages of COFs, such as weak interfacial contact with antibiotics, light response limitation, charge-carrier recombination, and low oxygen activation efficiency, limit their practical application in the photocatalytic degradation of antibiotics. On this basis, PyTTA-COF-OH via good crystallinity and hydrophilicity was constructed through the synergistic strategy combining hydroxylation modulation of the surface microenvironment and expansion of the π-conjugated structure. Simultaneously, Surface hydroxyl functionalization of PyTTA-COF-OH not only reduced the band gap width but also enhanced the light absorption in the visible band. Significantly, theoretical calculations indicated that the introduction of hydroxyl groups widened the electrostatic potential difference within the molecular structure, further promoting exciton dissociation and charge separation. PyTTA-COF-OH removed sulfadiazine (SDZ) up to 99% in 10 mg/L SDZ solution. Besides, the results of the interference experiments and the cycling experiments proved that PyTTA-COF-OH had better anti-interference and stability. Based on the mechanistic analysis, the surface hydroxyl–functionalized PyTTA-COF-OH effectively promoted the adsorption of oxygen and the transfer of electrons to the adsorbed oxygen, thus increasing the efficiency of the O₂^•- generation, aiming at the efficient degradation of antibiotics under the visible light conditions.
- COFs,
- Antibiotics,
- Photocatalytic,
- Hydroxylation,
- Sulfadiazine
1. [1]
  D.G.J. Larsson, C.F. Flach, Nat. Rev. Microbiol. 20 (2022) 257–269. doi: 10.1038/s41579-021-00649-x
2. [2]
  K. Zhu, X. Li, Y. Chen, et al., Coordin. Chem. Rev. 510 (2024) 215813. doi: 10.1016/j.ccr.2024.215813
3. [3]
  Y. Wang, D. Li, X. Ge, et al., Adv. Mater. 36 (2024) 2402935. doi: 10.1002/adma.202402935
4. [4]
  W. Yu, N. Fang, R. Wang, et al., Adv. Funct. Mater. 34 (2023) 2314894.
5. [5]
  Z. Zhang, J. Liang, W. Zhang, et al., Appl. Catal. B: Environ. Energy 330 (2023) 122621. doi: 10.1016/j.apcatb.2023.122621
6. [6]
  J. Peng, P. Zhou, H. Zhou, et al., Environ. Sci. Technol. 57 (2023) 10804–10815. doi: 10.1021/acs.est.2c08266
7. [7]
  C. Qin, Y. Yang, X. Wu, et al., Nat. Commun. 14 (2023) 6740. doi: 10.1038/s41467-023-42513-x
8. [8]
  Y. Tao, Y. Hou, H. Yang, et al., Proc. Natl. Acad. Sci. U. S. A. 121 (2024) e2401175121. doi: 10.1073/pnas.2401175121
9. [9]
  X. Bai, X. Liu, R. Zong, Appl. Catal. B: Environ. Energy 366 (2025) 125062. doi: 10.1016/j.apcatb.2025.125062
10. [10]
  S. Deng, W.P. Xiong, G.X. Zhang, et al., Adv. Energy Mater. 14 (2024) 2401768. doi: 10.1002/aenm.202401768
11. [11]
  Y. Hou, P. Zhou, F. Liu, et al., Nat. Commun. 15 (2024) 7350. doi: 10.1038/s41467-024-51878-6
12. [12]
  C. Tang, M. Cheng, C. Lai, et al., Coordin. Chem. Rev. 474 (2023) 214846. doi: 10.1016/j.ccr.2022.214846
13. [13]
  X. Yang, L. Sheng, Y. Ye, et al., J. Mater. Sci. Technol. 150 (2023) 11–26. doi: 10.1016/j.jmst.2022.10.092
14. [14]
  S. Han, Z. Li, S. Ma, et al., J. Mater. Chem. A 9 (2021) 3333–3340. doi: 10.1039/d0ta10232f
15. [15]
  H. Yang, D. He, L. Fan, et al., Adv. Mater. 37 (2025) 2410221. doi: 10.1002/adma.202410221
16. [16]
  R. Liu, K.T. Tan, Y. Gong, et al., Chem. Soc. Rev. 50 (2021) 120–242. doi: 10.1039/d0cs00620c
17. [17]
  B. Mishra, A. Alam, A. Chakraborty, et al., Adv. Mater. 37 (2025) 2413118. doi: 10.1002/adma.202413118
18. [18]
  T. He, Y. Zhao, Angew. Chem. Int. Ed. 62 (2023) e202303086. doi: 10.1002/anie.202303086
19. [19]
  Y. Zhang, X. Guan, Z. Meng, et al., J. Am. Chem. Soc. 147 (2025) 3776–3785. doi: 10.1021/jacs.4c16538
20. [20]
  A. López-Magano, S. Daliran, A.R. Oveisi, et al., Adv. Mater. 35 (2023) 2209475. doi: 10.1002/adma.202209475
21. [21]
  H. Wang, H. Wang, Z. Wang, et al., Chem. Soc. Rev. 49 (2020) 4135–4165. doi: 10.1039/d0cs00278j
22. [22]
  Y. Hou, F. Liu, B. Zhang, et al., Environ. Sci. Technol. 56 (2022) 16303–16314. doi: 10.1021/acs.est.2c06056
23. [23]
  X. Gu, H. Zhai, S. Cheng, Water Res. 190 (2021) 116762. doi: 10.1016/j.watres.2020.116762
24. [24]
  R. Zandipak, N. Bahramifar, M. Torabi, et al., Chem. Eng. J. 494 (2024) 152843. doi: 10.1016/j.cej.2024.152843
25. [25]
  Q.Y. Wang, J. Liu, M. Cao, et al., Angew. Chem. Int. Ed. 61 (2022) e202207130. doi: 10.1002/anie.202207130
26. [26]
  Z.B. Zhou, P.J. Tian, J. Yao, et al., Nat. Commun. 13 (2022) 2180. doi: 10.1038/s41467-022-29814-3
27. [27]
  J. Yang, S. Tian, Z. Song, et al., Coordin. Chem. Rev. 523 (2025) 216257.
28. [28]
  X. Bai, L. Guo, T. Jia, et al., J. Mater. Chem. A 12 (2024) 13116–13126. doi: 10.1039/d4ta01785d
29. [29]
  T. Wang, A. Kumar, G. Sharma, et al., npj Clean Water 7 (2024) 97. doi: 10.1038/s41545-024-00393-8
30. [30]
  Y. Yao, C. Zhu, R. Liu, et al., Small 20 (2024) 2404885. doi: 10.1002/smll.202404885
31. [31]
  Y.Y. Gu, J. Wang, Q. Tang, et al., ACS Catal. 14 (2024) 11262–11272. doi: 10.1021/acscatal.4c02827
32. [32]
  S. Karak, K. Dey, R. Banerjee, Adv. Mater. 34 (2022) 2202751.
33. [33]
  J. Cheng, Y. Wu, W. Zhang, et al., Adv. Mater. 36 (2024) 2305313. doi: 10.1002/adma.202305313
34. [34]
  J. Sun, H. Sekhar Jena, C. Krishnaraj, et al., Angew. Chem. Int. Ed. 62 (2023) e202216719. doi: 10.1002/anie.202216719
35. [35]
  K. Huang, J. Bai, R. Shen, et al., Adv. Funct. Mater. 33 (2023) 2307300. doi: 10.1002/adfm.202307300
36. [36]
  J. Sun, L. Peng, Y. Liu, et al., Chem. Mater. 36 (2024) 3666–3672. doi: 10.1021/acs.chemmater.3c03168
37. [37]
  Z. Li, Z. Dong, Z. Zhang, et al., Angew. Chem. Int. Ed. 64 (2025) e202420218. doi: 10.1002/anie.202420218
38. [38]
  P. Dong, C. Wang, L. Zhang, et al., ACS Catal. 14 (2024) 17794–17805. doi: 10.1021/acscatal.4c04968
39. [39]
  X. Chen, M. Addicoat, E. Jin, et al., J. Am. Chem. Soc. 137 (2015) 3241–3247. doi: 10.1021/ja509602c
40. [40]
  T. Yang, F. Kong, Y. Chen, et al., Angew. Chem. Int. Ed. 64 (2025) e202424110. doi: 10.1002/anie.202424110
41. [41]
  L. Li, X. Lv, Y. Xue, et al., Angew. Chem. Int. Ed. 63 (2024) e202320218. doi: 10.1002/anie.202320218
42. [42]
  C. Yang, S. Wan, B. Zhu, J. Yu, et al., Angew. Chem. Int. Ed. 61 (2022) e202208438.
43. [43]
  J. Xu, W. Li, W. Liu, et al., Angew. Chem. Int. Ed. 61 (2022) e202212243.
44. [44]
  H. Zhang, L. Zhang, S. Dong, et al., J. Hazard. Mater. 466 (2023) 130756.
45. [45]
  N.E. Powers-Riggs, X. Zuo, R.M. Young, et al., J. Am. Chem. Soc. 141 (2019) 17512–17516. doi: 10.1021/jacs.9b10108
46. [46]
  Z. Lu, R. Zhao, H. Yang, et al., Angew. Chem. Int. Ed. 61 (2022) e202208898.
47. [47]
  C. Wu, Z. Teng, C. Yang, et al., Adv. Mater. 34 (2022) 2110266.
48. [48]
  Y. Han, W. Zhang, J. Lei, et al., Appl. Catal. B: Environ. Energy 364 (2025) 124849.
49. [49]
  Z. Weng, Y. Lin, S. Guo, et al., Angew. Chem. Int. Ed. 62 (2023) e202310934.
50. [50]
  R. Ruiz-González, R. Bresolí-Obach, Ò. Gulías, et al., Angew. Chem. Int. Ed. 56 (2017) 2885–2888. doi: 10.1002/anie.201609050
51. [51]
  Y. Guo, J. Zhan, G. Yu, et al., Water Res. 194 (2021) 116927.
52. [52]
  J.H. Wu, H.Q. Yu, Environ. Sci. Technol. 58 (2024) 18496–18507. doi: 10.1021/acs.est.4c06725
53. [53]
  X. Dong, F. Zhang, Y. Wang, et al., Appl. Catal. B: Environ. Energy 345 (2024) 123660.
54. [54]
  P. Zhang, Y. Tong, Y. Liu, et al., Angew. Chem. Int. Ed. 59 (2020) 16209–16217. doi: 10.1002/anie.202006747
55. [55]
  Y. Qian, D. Li, Y. Han, et al., J. Am. Chem. Soc. 142 (2020) 20763–20771. doi: 10.1021/jacs.0c09727
1. [1]
  Zhiling Du , Zhiqi Zhou , Nan Sun , Cailiang Yue , Fuqiang Liu . Pyromellitic diimide induced TiO₂ mesocrystals with oxygen vacancies for synergistic photocatalytic H₂O₂ production and antibiotics degradation. Chinese Chemical Letters, 2026, 37(3): 111341-. doi: 10.1016/j.cclet.2025.111341
2. [2]
  Kai Han , Guohui Dong , Ishaaq Saeed , Tingting Dong , Chenyang Xiao . Morphology and photocatalytic tetracycline degradation of g-C3N4 optimized by the coal gangue. Chinese Journal of Structural Chemistry, 2024, 43(2): 100208-100208. doi: 10.1016/j.cjsc.2023.100208
3. [3]
  Hai-Bo Huang , Fang-Long Sun , Ze Luo , Meng-Yu Sun , Ben-Hao Liu , Xu-Sheng Wang , Hua Tang . MOF@MOF hierarchical heterotructures for enhanced photocatalytic H2O2 production and furfuryl alcohol oxidation. Chinese Journal of Structural Chemistry, 2025, 44(11): 100717-100717. doi: 10.1016/j.cjsc.2025.100717
4. [4]
  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
5. [5]
  Yuxin Li , Chengbin Liu , Qiuju Li , Shun Mao . Fluorescence analysis of antibiotics and antibiotic-resistance genes in the environment: A mini review. Chinese Chemical Letters, 2024, 35(10): 109541-. doi: 10.1016/j.cclet.2024.109541
6. [6]
  Zhiqiang Liu , Qiang Gao , Wei Shen , Meifeng Xu , Yunxin Li , Weilin Hou , Hai-Wei Shi , Yaozuo Yuan , Erwin Adams , Hian Kee Lee , Sheng Tang . Removal and fluorescence detection of antibiotics from wastewater by layered double oxides/metal-organic frameworks with different topological configurations. Chinese Chemical Letters, 2024, 35(8): 109338-. doi: 10.1016/j.cclet.2023.109338
7. [7]
  Jinshuai Zheng , Junfeng Niu , Crispin Halsall , Yadi Guo , Peng Zhang , Linke Ge . New insights into transformation mechanisms for sulfate and chlorine radical-mediated degradation of sulfonamide and fluoroquinolone antibiotics. Chinese Chemical Letters, 2025, 36(5): 110202-. doi: 10.1016/j.cclet.2024.110202
8. [8]
  Chao-Long Chen , Rong Chen , La-Sheng Long , Lan-Sun Zheng , Xiang-Jian Kong . Anchoring heterometallic cluster on P-doped carbon nitride for efficient photocatalytic nitrogen fixation in water and air ambient. Chinese Chemical Letters, 2024, 35(4): 108795-. doi: 10.1016/j.cclet.2023.108795
9. [9]
  Yueying Wang , Jianming Xiong , Linwei Xin , Yuanyuan Li , He Huang , Wenjun Miao . Photosensitizer-synergized g-carbon nitride nanosheets with enhanced photocatalytic activity for eradicating drug-resistant bacteria and promoting wound healing. Chinese Chemical Letters, 2025, 36(4): 110003-. doi: 10.1016/j.cclet.2024.110003
10. [10]
  Qiang Feng , Jindong Hao , Ya Hu , Rong Fu , Wei Wei , Dong Yi . Photocatalytic multi-component synthesis of ester-containing quinoxalin-2(1H)-ones using water as the hydrogen donor. Chinese Chemical Letters, 2025, 36(6): 110582-. doi: 10.1016/j.cclet.2024.110582
11. [11]
  Pengkun Li , Runjie Wu , Shuai Gao , Zeping Qin , Mingming Sun , Changzheng Wang , Wenming Sun , Qiang Wang . Bi-Bi₂Ti₂O₇ ohmic junction: Dual electron channels driving efficient photocatalytic nitrogen fixation. Chinese Chemical Letters, 2026, 37(1): 111116-. doi: 10.1016/j.cclet.2025.111116
12. [12]
  Lanxin Wang , Kaiwei Liang , Xuelian Yu , Guocheng Lv , Libing Liao . Facile method for creating frustrated Lewis pairs in g-C₃N₄ to enhance photocatalytic nitrogen fixation performance. Chinese Chemical Letters, 2026, 37(1): 110572-. doi: 10.1016/j.cclet.2024.110572
13. [13]
  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
14. [14]
  Wan-Yin Gao , Xiao-Qiang Cao , Li-Fei Hou , Hao-Yun Lu , Zhao-Jing Zhu , Wen-Jia Kong , Yang Zhang , Yi-Zhen Zhang , Ya-Nan Shang , Xing Xu . Electron transfer chemistry triggered by silicon-doped carbon catalysts derived from natural minerals for the degradation of organic pollutants. Chinese Chemical Letters, 2026, 37(1): 111095-. doi: 10.1016/j.cclet.2025.111095
15. [15]
  Han Yan , Xudong Yang , Wen Liu , Fengbin Sun , Guodong Jia . Biochar-supported amorphous ferric hydroxide for peracetic acid activation to degrade cefapirin in water: The crucial roles of iron and nitrogen. Chinese Chemical Letters, 2026, 37(3): 111542-. doi: 10.1016/j.cclet.2025.111542
16. [16]
  Yu Wang , Changjiang Lu , Danhua Jiao , Fei Wang , Xiaojian Gong , Tianhua Yu , Anping Wang , Chong-Chen Wang . Efficient degradation of tetracycline hydrochloride via high-redox S-scheme MOF-on-MOF heterojunction catalyst. Chinese Chemical Letters, 2026, 37(6): 111979-. doi: 10.1016/j.cclet.2025.111979
17. [17]
  Feng Cui , Fangman Chen , Xiaochun Xie , Chenyang Guo , Kai Xiao , Ziping Wu , Yinglu Chen , Junna Lu , Feixia Ruan , Chuanxu Cheng , Chao Yang , Dan Shao . Scalable production of mesoporous titanium nanoparticles through sequential flash nanocomplexation. Chinese Chemical Letters, 2024, 35(4): 108681-. doi: 10.1016/j.cclet.2023.108681
18. [18]
  Haojie Song , Laiyu Luo , Siyu Wang , Guo Zhang , Baojiang Jiang . Advances in poly(heptazine imide)/poly(triazine imide) photocatalyst. Chinese Chemical Letters, 2024, 35(10): 109347-. doi: 10.1016/j.cclet.2023.109347
19. [19]
  Ming-Zhen Li , Yang Zhang , Kun Li , Ya-Nan Shang , Yi-Zhen Zhang , Yu-Jiao Kan , Zhi-Yang Jiao , Yu-Yuan Han , Xiao-Qiang Cao . In situ regeneration of catalyst for Fenton-like degradation by photogenerated electron transportation: Characterization, performance and mechanism comparison. Chinese Chemical Letters, 2025, 36(1): 109885-. doi: 10.1016/j.cclet.2024.109885
20. [20]
  Zhimin Yuan , Xingling Zhao , Xianglin Zhu , Kaili Wang , Ya-Qian Lan , Zaiyong Jiang . Solar-driven hydrogen peroxide production on designed g-C₃N₄: Strategies, mechanisms, and perspectives. Chinese Chemical Letters, 2026, 37(6): 112572-. doi: 10.1016/j.cclet.2026.112572

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(15)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142