Citation: Shuangyu Wu, Jian Peng, Yue Jiang, Sijie Lin. The overlooked promotional effects of alcohols to BiOBr catalysts in photocatalytic degradation of organic pollutants[J]. Chinese Chemical Letters, ;2025, 36(11): 110819. doi: 10.1016/j.cclet.2025.110819 shu

The overlooked promotional effects of alcohols to BiOBr catalysts in photocatalytic degradation of organic pollutants

Shuangyu Wu ^{a, b} ,
Jian Peng ^{a, b} ,
Yue Jiang ^{a, b} ,
Sijie Lin ^{a, b, *,}

a.
College of Environmental Science and Engineering, Biomedical Multidisciplinary Innovation Research Institute, Shanghai East Hospital, Tongji University, Shanghai 200092, China
b.
Key Laboratory of Yangtze River Water Environment, Shanghai Institute of Pollution Control and Ecological Security, Tongji University, Shanghai 200092, China

lin.sijie@tongji.edu.cn

Received Date: 10 September 2024
Revised Date: 13 November 2024
Accepted Date: 2 January 2025
Available Online: 2 January 2025

Figures(4)

Alcohols are often used as scavengers to identify the contribution of radicals for contaminant degradation in heterogeneous catalysis. The generation of alcohol radicals is often overlooked, leading to misinterpretation of degradation mechanisms and alcohol's role. Herein, a series of bismuth oxybromide (BiOBr) with varying amounts of active species was synthesized as representative catalysts to elucidate the role of alcohols in heterogeneous catalysis. Among various alcohols, isopropanol (IPA) was found to significantly enhance the photocatalytic degradation of carbamazepine (CBZ) by BiOBr. Electron paramagnetic resonance results confirmed that IPA was oxidized to alcohol radicals by BiOBr. The promotional effect of IPA was due to the generation of H₂O₂ through the reaction between alcohol radicals and dissolved oxygen. H₂O₂ subsequently led to the production of superoxide anion, the dominant radical in CBZ degradation. The promotional effect was also observed with other alcohols. The bond dissociation energy of the C–H bond adjacent to the hydroxyl group in alcohols determined the extent of promotion, while other characteristics such as the number of hydroxyl groups did not. Higher bond dissociation energy corresponded to a greater promotional effect. This study clarifies the inconsistent observations resulting from the use of various alcohols in heterogeneous catalysis and provides new insights into the overlooked role of alcohols.
- Alcohol radical,
- Scavenger,
- Promoter,
- Heterogeneous catalysis,
- BiOBr
1. [1]
  C. Huang, W. Dai, S. Deng, et al., Chin. Chem. Lett. 35 (2024) 109429.
2. [2]
  B.A. Wols, C.H.M. Hofman-Caris, Water Res. 46 (2012) 2815-2827.
3. [3]
  B.P. Chaplin, Environ Sci-Proc. Imp. 16 (2014) 1182-1203.
4. [4]
  X. Qu, P.J.J. Alvarez, Q. Li, Water Res. 47 (2013) 3931-3946.
5. [5]
  Y. Jiang, Y. Qin, T. Yu, S. Lin, Chin. Chem. Lett. 32 (2021) 1823-1826.
6. [6]
  L. Wang, Q. Zhang, B. Chen, et al., Water Res. 174 (2020) 115605.
7. [7]
  K. Makino, M.M. Mossoba, P. Riesz, J. Phys. Chem. 87 (1983) 1369-1377. doi: 10.1021/j100231a020
8. [8]
  T. Berndt, S. Richters, T. Jokinen, et al., Nat. Commun. 7 (2016) 13677.
9. [9]
  C. Qin, J. Tang, R. Qiao, S. Lin, Chin. Chem. Lett. 33 (2022) 5218-5222.
10. [10]
  Y. Jiang, D. Baimanov, S. Jin, et al., Proc. Nat. Acad. Sci. U. S. A. 120 (2023) e2210211120.
11. [11]
  G. Heit, A. Neuner, P.Y. Saugy, A.M. Braun, J. Phys. Chem. A 102 (1998) 5551-5561.
12. [12]
  E. Popov, M. Mametkuliyev, D. Santoro, L. Liberti, J. Eloranta, Environ. Sci. Technol. 44 (2010) 7827-7832. doi: 10.1021/es101959y
13. [13]
  L. Wang, B. Li, D.D. Dionysiou, et al., Environ. Sci. Technol. 56 (2022) 3386-3396. doi: 10.1021/acs.est.1c03796
14. [14]
  L. Ding, Y. Hou, H. Liu, et al., ACS ES&T Water 3 (2023) 3534-3543. doi: 10.1021/acsestwater.3c00271
15. [15]
  H.A. Schwarz, R.W. Dodson, J. Phys. Chem. 93 (1989) 409-414. doi: 10.1021/j100338a079
16. [16]
  C. Zhu, F. Zhu, D.D. Dionysiou, et al., Water Res. 139 (2018) 66-73.
17. [17]
  X. Wang, D. Si, Y. Li, et al., Water Res. 245 (2023) 120557.
18. [18]
  Y. Chen, M. Xu, J. Wen, et al., Nat. Sustain. 4 (2021) 618-626. doi: 10.1038/s41893-021-00697-4
19. [19]
  X. Chen, S. Guan, J. Zhou, et al., Angew. Chem. Int. Ed. 62 (2023) e202312734.
20. [20]
  Y. Chen, S. Guan, H. Ge, et al., Angew. Chem. Int. Ed. 61 (2022) e202213640.
21. [21]
  H. Shang, Y. Chen, S. Guan, et al., Nat. Chem. Eng. 1 (2024) 170-179. doi: 10.1038/s44286-023-00026-w
22. [22]
  J. Cao, Z. Xu, Y. Chen, et al., Angew. Chem. Int. Ed. 62 (2023) e202302202.
23. [23]
  W. Jones, D.J. Martin, A. Caravaca, et al., Appl. Catal. B: Environ. 240 (2019) 373-379.
24. [24]
  M. Teranishi, S.I. Naya, H. Tada, J. Phys. Chem. C 120 (2016) 1083-1088. doi: 10.1021/acs.jpcc.5b10626
25. [25]
  G. Ren, M. Shi, Z. Li, Z. Zhang, X. Meng, Appl. Catal. B: Environ. 327 (2023) 122462.
26. [26]
  J. Di, J. Xia, H. Li, S. Guo, S. Dai, Nano Energy 41 (2017) 172-192.
27. [27]
  X. Xue, R. Chen, H. Chen, et al., Nano Lett. 18 (2018) 7372-7377. doi: 10.1021/acs.nanolett.8b03655
28. [28]
  X. Shi, P. Wang, W. Li, et al., Appl. Catal. B: Environ. 243 (2019) 322-329.
29. [29]
  S. Zhang, G. Hu, M. Chen, et al., Appl. Catal. B: Environ. 330 (2023) 122584.
30. [30]
  S. Zhang, X. Yi, G. Hu, et al., Coord. Chem. Rev. 478 (2023) 214970.
31. [31]
  H. Tan, Z. Zhao, W.B. Zhu, et al., ACS Appl. Mater. 6 (2014) 19184-19190. doi: 10.1021/am5051907
32. [32]
  X. Tong, X. Cao, T. Han, et al., Nano Res. 12 (2019) 1625-1630. doi: 10.1007/s12274-018-2404-x
33. [33]
  M. Shi, G. Li, J. Li, et al., Angew. Chem. Int. Ed. 59 (2020) 6590-6595. doi: 10.1002/anie.201916510
34. [34]
  J. Wu, X. Li, W. Shi, et al., Angew. Chem. Int. Ed. 57 (2018) 8719-8723. doi: 10.1002/anie.201803514
35. [35]
  X. Ren, M. Gao, Y. Zhang, et al., Appl. Catal. B: Environ. 274 (2020) 119063.
36. [36]
  Z. Miao, Q. Wang, Y. Zhang, L. Meng, X. Wang, Appl. Catal. B: Environ. 301 (2022) 120802.
37. [37]
  S. Xi, J. Xue, F. Wang, X. Li, J. Phys. Chem. A 125 (2021) 5423-5437. doi: 10.1021/acs.jpca.1c00784
38. [38]
  B.R. Müller, S. Majoni, D. Meissner, R. Memming, J Photoch Photobio A 151 (2002) 253-265.
39. [39]
  K. Sathiyan, R. Bar-Ziv, V. Marks, D. Meyerstein, T. Zidki, Chem. Eur. J. 27 (2021) 15936-15943. doi: 10.1002/chem.202103040
40. [40]
  G.D. Fang, D.D. Dionysiou, S.R. Al-Abed, D.M. Zhou, Appl. Catal. B: Environ. 129 (2013) 325-332.
41. [41]
  M.N. Schuchmann, C. Von Sonntag, J. Phys. Chem. 83 (1979) 780-784. doi: 10.1021/j100470a004
42. [42]
  Z. Gao, D. Zhang, Y.S. Jun, Environ. Sci. Technol. 55 (2021) 10442-10450. doi: 10.1021/acs.est.1c01578
43. [43]
  J. Peng, Y. Jiang, S. Wu, et al., Chin. Chem. Lett. 35 (2023) 108903.
44. [44]
  W. Zhang, W. Huang, J. Jin, Y. Gan, S. Zhang, Appl. Catal. B: Environ. 292 (2021) 120197.
45. [45]
  G. Tan, L. She, T. Liu, et al., Appl. Catal. B: Environ. 207 (2017) 120-133.
46. [46]
  V.B. Oyeyemi, J.A. Keith, E.A. Carter, J. Phys. Chem. A 118 (2014) 3039-3050. doi: 10.1021/jp501636r
47. [47]
  T. Newhouse, P.S. Baran, Angew. Chem. Int. Ed. 50 (2011) 3362-3374. doi: 10.1002/anie.201006368
48. [48]
  I.A. Shkrob, M.C. Sauer, D. Gosztola, J. Phys. Chem. B 108 (2004) 12512-12517.
49. [49]
  S. Goldstein, D. Aschengrau, Y. Diamant, J. Rabani, Environ. Sci. Technol. 41 (2007) 7486-7490. doi: 10.1021/es071379t
50. [50]
  O.C. Zafiriou, Mar. Chem. 30 (1990) 31-43.
1. [1]
  Siyang Xue , Chen Cheng , Jieqiong Kang , Kaixuan Zheng , Adela Jing Li , Renli Yin . Oxygen vacancies-rich BiOBr bridged direct electron transfer with peroxymonosulfate for integrating superoxide radical and singlet oxygen on selective pollutants degradation. Chinese Chemical Letters, 2025, 36(10): 110776-. doi: 10.1016/j.cclet.2024.110776
2. [2]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
3. [3]
  Jin ZHANG , Yuting WANG , Bin YU , Yuxin ZHONG , Yufeng ZHANG . Corn straw-derived carbon/BiOBr composite: Synthesis and photocatalytic degradation performance for rhodamine B. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1397-1408. doi: 10.11862/CJIC.20250028
4. [4]
  Xiaofan ZHANG , Yu DUAN , Meijie SHI , Nan LU , Renhong LI , Xiaoqing YAN . Z-scheme Co₃O₄/BiOBr heterojunction for efficient photoreduction CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1878-1888. doi: 10.11862/CJIC.20250079
5. [5]
  Yujia LI , Tianyu WANG , Fuxue WANG , Chongchen WANG . Direct Z-scheme MIL-100(Fe)/BiOBr heterojunctions: Construction and photo-Fenton degradation for sulfamethoxazole. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 481-495. doi: 10.11862/CJIC.20230314
6. [6]
  Ruiying Liu , Li Zhao , Baishan Liu , Jiayuan Yu , Yujie Wang , Wanqiang Yu , Di Xin , Chaoqiong Fang , Xuchuan Jiang , Riming Hu , Hong Liu , Weijia Zhou . Modulating pollutant adsorption and peroxymonosulfate activation sites on Co3O4@N,O doped-carbon shell for boosting catalytic degradation activity. Chinese Journal of Structural Chemistry, 2024, 43(8): 100332-100332. doi: 10.1016/j.cjsc.2024.100332
7. [7]
  Heng Yang , Zhijie Zhou , Conghui Tang , Feng Chen . Recent advances in heterogeneous hydrosilylation of unsaturated carbon-carbon bonds. Chinese Chemical Letters, 2024, 35(6): 109257-. doi: 10.1016/j.cclet.2023.109257
8. [8]
  Shuai Tang , Zian Wang , Mengyi Zhu , Xinyun Zhao , Xiaoyun Hu , Hua Zhang . Synthesis of organoboron compounds via heterogeneous C–H and C–X borylation. Chinese Chemical Letters, 2025, 36(5): 110503-. doi: 10.1016/j.cclet.2024.110503
9. [9]
  Wen-Jing Li , Jun-Bo Wang , Yu-Heng Liu , Mo Zhang , Zhan-Hui Zhang . Molybdenum-doped carbon nitride as an efficient heterogeneous catalyst for direct amination of nitroarenes with arylboronic acids. Chinese Chemical Letters, 2025, 36(3): 110001-. doi: 10.1016/j.cclet.2024.110001
10. [10]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
11. [11]
  Hua Liu , Jian Zhao , Qi Li , Xiang-Yu Zhang , Zhi-Wei Zheng , Kun Huang , Da-Bin Qin , Bin Zhao . Indium-captured zirconium-porphyrin frameworks displaying rare multi-selectivity for catalytic transfer hydrogenation of aldehydes and ketones. Chinese Chemical Letters, 2025, 36(6): 110593-. doi: 10.1016/j.cclet.2024.110593
12. [12]
  Chengyao Zhao , Jingyuan Liao , Yuxiang Zhu , Yiying Zhang , Lianjie Zhai , Junrong Huang , Hengzhi You . Polystyrene-supported phosphoric-acid catalyzed atroposelective construction of axially chiral N-aryl benzimidazoles. Chinese Chemical Letters, 2025, 36(6): 110337-. doi: 10.1016/j.cclet.2024.110337
13. [13]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
14. [14]
  Honghong Zhang , Zhen Wei , Derek Hao , Lin Jing , Yuxi Liu , Hongxing Dai , Weiqin Wei , Jiguang Deng . 非均相催化CO₂与烃类协同催化转化的最新进展. Acta Physico-Chimica Sinica, 2025, 41(7): 100073-0. doi: 10.1016/j.actphy.2025.100073
15. [15]
  Yongqing Xu , Yuyao Yang , Mengna Wu , Xiaoxiao Yang , Xuan Bie , Shiyu Zhang , Qinghai Li , Yanguo Zhang , Chenwei Zhang , Robert E. Przekop , Bogna Sztorch , Dariusz Brzakalski , Hui Zhou . Review on Using Molybdenum Carbides for the Thermal Catalysis of CO₂ Hydrogenation to Produce High-Value-Added Chemicals and Fuels. Acta Physico-Chimica Sinica, 2024, 40(4): 2304003-0. doi: 10.3866/PKU.WHXB202304003
16. [16]
  Xiang Li , Beibei Zhang , Zhixiang Wang , Xiangyu Chen . Organocatalyzed iodine-mediated reversible-deactivation radical polymerization via photoinduced charge transfer complex catalysis. Chinese Chemical Letters, 2025, 36(6): 110383-. doi: 10.1016/j.cclet.2024.110383
17. [17]
  Pei Xu , Tian-Zi Hao , Zhi-Tao Liu , Yi-Qin Liu , Hui-Xian Jiang , Dong Guo , Xu Zhu . Visible-light-induced dual catalysis for divergent reduction of nitro compounds with CO₂ radical anion. Chinese Chemical Letters, 2025, 36(10): 110899-. doi: 10.1016/j.cclet.2025.110899
18. [18]
  Hongping Zhao , Weiming Yuan . Merging catalytic electron donor-acceptor complex and copper catalysis: Enantioselective radical carbocyanation of alkenes. Chinese Chemical Letters, 2025, 36(10): 110894-. doi: 10.1016/j.cclet.2025.110894
19. [19]
  Xingmin Chen , Yunyun Wu , Yao Tang , Peishen Li , Shuai Gao , Qiang Wang , Wen Liu , Sihui Zhan . Construction of Z-scheme Cu-CeO₂/BiOBr heterojunction for enhanced photocatalytic degradation of sulfathiazole. Chinese Chemical Letters, 2024, 35(7): 109245-. doi: 10.1016/j.cclet.2023.109245
20. [20]
  Xianghai Song , Xiaoying Liu , Zhixiang Ren , Xiang Liu , Mei Wang , Yuanfeng Wu , Weiqiang Zhou , Zhi Zhu , Pengwei Huo . Insights into the greatly improved catalytic performance of N-doped BiOBr for CO₂ photoreduction. Acta Physico-Chimica Sinica, 2025, 41(6): 100055-0. doi: 10.1016/j.actphy.2025.100055

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(23)
HTML views(3)

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