Citation: Yuhang Zhang, Haiming Cai, Chuling Guo, Guining Lu, Zhi Dang, Xiao Liu, Falong Jia, Zhihui Ai, Chunhua Feng. Sustainable molecular oxygen activation for efficient treatment of heavy-metal complexes by fissured-phosphorylated zero-valent iron[J]. Chinese Chemical Letters, ;2026, 37(8): 112353. doi: 10.1016/j.cclet.2025.112353 shu

Sustainable molecular oxygen activation for efficient treatment of heavy-metal complexes by fissured-phosphorylated zero-valent iron

Yuhang Zhang ^a ,
Haiming Cai ^a ,
Chuling Guo ^a ,
Guining Lu ^a ,
Zhi Dang ^{a, *,} ,
Xiao Liu ^b ,
Falong Jia ^{b, *,} ,
Zhihui Ai ^b ,
Chunhua Feng ^a

a.
The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, South China University of Technology, Guangzhou 510006, China
b.
College of Chemistry, Central China Normal University, Wuhan 430079, China

chzdang@scut.edu.cn

fljia@ccnu.edu.cn

Received Date: 30 September 2025
Revised Date: 12 December 2025
Accepted Date: 30 December 2025
Available Online: 31 December 2025

Figures(5)

Heavy metals complexed with organic reagents in wastewater jeopardize environmental safety, resist conventional removal methods, but are also valuable metallic resources. Herein, a novel fissured-phosphorylated zero-valent iron (P-ZVI^bm&ln) was synthesized via mechanochemical phosphorylation and liquid-nitrogen-quenching, and applied to benzohydroxamic acid-complexed Cu(Ⅱ) (Cu(Ⅱ)-BHA) degradation and synchronous copper recovery. During mechanochemical phosphorylation, a ferrous phosphate shell with abundant surface ferrous (≡Fe²⁺) was constructed on ZVI, which facilitated the activation of molecular oxygen into reactive oxygen species (ROS) for Cu(Ⅱ)-BHA degradation. Moreover, the subsequent liquid-nitrogen-quenching created surface cracks for more Fe⁰ cores exposure, which triggered the comproportionation reaction (Fe⁰ + 2Fe³⁺ → 3Fe²⁺), thereby strengthening Fe²⁺ regeneration and sustainable molecular oxygen activation for efficient oxidative decomplexation and metal recovery. In the P-ZVI^bm&ln/Cu(Ⅱ)-BHA decontamination process, nearly 100% of Cu was recovered and BHA was degraded, while P-ZVI^bm&ln showed excellent cyclic reaction performance. Through diverse experiments and density functional theory (DFT) calculations, researchers shed light on the mechanism. Meanwhile, the P-ZVI^bm&ln could effectively treat other metal-BHA complexes (e.g., Cr(Ⅲ), Mn(Ⅱ), Ni(Ⅱ), Ag(Ⅰ), Cd(Ⅱ), and Pb(Ⅱ)) and actual mine wastewater containing Cu(Ⅱ) complexes with satisfactory metal recovery, showing promising application prospects in treatment of heavy-metal complex wastewater and sustainable development.
1. [1]
  M.K. Li, J.Y. Wang, H.R. Shen, et al., Chem. Eng. J. 461 (2023) 142008. doi: 10.1016/j.cej.2023.142008
2. [2]
  M.Q. Li, N. Chen, H. Shang, et al., Technol, Environ. Sci. 56 (2022) 10945–10953. doi: 10.1021/acs.est.2c02363
3. [3]
  Y. Luo, H. Li, H.L. Yang, et al., Environ. Sci-Nano 5 (2024) 2091. doi: 10.1039/d3en00911d
4. [4]
  J.N. Zu, N.Q. Zhang, X.P. Liu, et al., Angew. Chem. Int. Ed. 64 (2025) e202415051. doi: 10.1002/anie.202415051
5. [5]
  J. Wang, J.Y. Cai, X.Q. Zhou, et al., Sep. Purif. Technol. 354 (2025) 128945. doi: 10.1016/j.seppur.2024.128945
6. [6]
  H.Y. Zhou, J.L. Peng, X.G. Duan, et al., Environ. Sci. Technol. 57 (2023) 3334–3344. doi: 10.1021/acs.est.2c07447
7. [7]
  Y.H. Zhang, H. Zhang, N.Q. Zhang, et al., Sep. Purif. Technol. 354 (2025) 128772. doi: 10.1016/j.seppur.2024.128772
8. [8]
  Z.S. Wang, L.J. Qiu, Y.H. Huang, et al., Chin. Chem. Lett. 35 (2024) 109195. doi: 10.1016/j.cclet.2023.109195
9. [9]
  X.Y. Zou, Y.H. Zhang, K. Wei, et al., J. Hazard. Mater. 446 (2023) 130752. doi: 10.1016/j.jhazmat.2023.130752
10. [10]
  C. Piña, H. Arriola, N. Nava, J. Phys. : Conf. Ser. 217 (2010) 012037. doi: 10.1088/1742-6596/217/1/012037
11. [11]
  E. Mattievich, J.A. Danon, J. Phys. Colloq. 37 (1976) 483–487.
12. [12]
  Y. Lv, L.T. Han, J. Shen, et al., Sep. Purif. Technol. 329 (2024) 125045. doi: 10.1016/j.seppur.2023.125045
13. [13]
  M.Q. Li, Y. Mu, H. Shang, et al., Appl. Catal. B: Environ. 263 (2020) 118364. doi: 10.1016/j.apcatb.2019.118364
14. [14]
  Z. Yang, X.W. Ma, C. Shan, et al., J. Hazard. Mater. 368 (2019) 698–704. doi: 10.1016/j.jhazmat.2019.01.105
15. [15]
  B. Özkaya, J. Hazard. Mater. 129 (2006) 158–163. doi: 10.1016/j.jhazmat.2005.08.025
16. [16]
  S. Lata, P.K. Singh, S.R. Samadder, Int. J. Environ. Sci. Technol. 12 (2015) 1461–1478. doi: 10.1007/s13762-014-0714-9
17. [17]
  S.H. Kow, M.R. Fahmi, C.Z.A. Abidin, S.A. Ong, N. Ibrahim, Desalin. Water Treat. 57 (2016) 29137–29142. doi: 10.1080/19443994.2016.1168133
18. [18]
  Y.H. Zhang, D.L. Li, L. She, et al., J. Hazard. Mater. 465 (2024) 133009. doi: 10.1016/j.jhazmat.2023.133009
19. [19]
  M.F. Luo, H. Zhang, J. Zhao, et al., ACS ES&T Engg. 3 (2023) 64–72. doi: 10.1021/acsestengg.2c00245
20. [20]
  W.X. Zheng, X. Luo, H.Y. Fu, et al., Environ. Sci. Technol. 58 (27) (2024) 12212–12224. doi: 10.1021/acs.est.4c02061
21. [21]
  E. -T. Yun, J.H. Lee, J. Kim, H. -D. Park, J. Lee, Environ. Sci. Technol. 52 (2018) 7032–7042. doi: 10.1021/acs.est.8b00959
22. [22]
  W.S. Li, Z.Q. Sun, Y.D. Chen, et al., Chin. Chem. Lett. 37 (2026) 111791. doi: 10.1016/j.cclet.2025.111791
23. [23]
  X. Zhang, H.W. Sun, Y.B. Shi, et al., Water Res. 235 (2023) 119828. doi: 10.1016/j.watres.2023.119828
24. [24]
  M.Z. Liao, S.X. Zhao, K. Wei, H.W. Sun, L.Z. Zhang, Appl. Catal. B: Environ. 330 (2023) 122619. doi: 10.1016/j.apcatb.2023.122619
25. [25]
  J. Koo, B.S. Bae, H.K. Na, J. Non-Cryst. Solids 212 (1997) 173–179. doi: 10.1016/S0022-3093(96)00651-5
26. [26]
  M.A. Ibrahim, A.M. Nada, D.E. Kamal, Indian J. Pure Appl. Phys. 43 (2005) 911–917.
27. [27]
  Z. Wei, Y.H. Hu, H.S. Han, W. Sun, J. Colloid Interface Sci. 562 (2020) 342–351. doi: 10.1016/j.jcis.2019.11.115
28. [28]
  Y.M. Wei, P. Song, Y. Wen, et al., Water Res. 268 (2025) 122656. doi: 10.1016/j.watres.2024.122656
29. [29]
  Z.P. Yang, Y.B. Shi, H. Li, et al., Environ. Sci. Technol. 56 (2022) 3587–3595. doi: 10.1021/acs.est.1c08532
1. [1]
  Yan Zhang , Shuo Chen , Huihui Peng , Ankang Wang , Yiming Sun , Chenying Zhou , Shuang Meng , Chuanshu He , Peng Zhou , Bo Lai . Treatment of nitrogen-contained refractory organic wastewater by micron zero-valent iron based two-stage process: Synergistic contaminant degradation and ammonia nitrogen formation. Chinese Chemical Letters, 2026, 37(7): 112209-. doi: 10.1016/j.cclet.2025.112209
2. [2]
  Chong-Chen Wang , Xiaohang Xu . Metal-organic frameworks helping resource and energy recovery from sludge. Chinese Chemical Letters, 2025, 36(10): 111287-. doi: 10.1016/j.cclet.2025.111287
3. [3]
  Zhongsen Wang , Lijun Qiu , Yunhua Huang , Meng Zhang , Xi Cai , Fanyu Wang , Yang Lin , Yanbiao Shi , Xiao Liu . Alcohothermal synthesis of sulfidated zero-valent iron for enhanced Cr(Ⅵ) removal. Chinese Chemical Letters, 2024, 35(7): 109195-. doi: 10.1016/j.cclet.2023.109195
4. [4]
  Yayu Dong , Jinghan Hao , Yingcai Wang , Xiaohong Cao , Zhimin Dong , Zhibin Zhang , Yunhai Liu . Recent advances in polyoxometalate-based functional materials for sustainable remediation of radionuclide and heavy metal pollution. Chinese Chemical Letters, 2026, 37(7): 111564-. doi: 10.1016/j.cclet.2025.111564
5. [5]
  Shili Wang , Mamitiana Roger Razanajatovo , Xuedong Du , Shunli Wan , Xin He , Qiuming Peng , Qingrui Zhang . Recent advances on decomplexation mechanisms of heavy metal complexes in persulfate-based advanced oxidation processes. Chinese Chemical Letters, 2024, 35(6): 109140-. doi: 10.1016/j.cclet.2023.109140
6. [6]
  Zi-Hao Zuo , Jiang-Kui Hu , Xi-Long Wang , Shi-Jie Yang , Wei-Qi Mai , Yao-Hui Zhu , Zheng Liao , Jia Liu , Hong Yuan , Jia-Qi Huang . Oxygen defect-mediated Li-ion transport for long-cycle solid-state lithium metal batteries. Chinese Chemical Letters, 2026, 37(5): 110851-. doi: 10.1016/j.cclet.2025.110851
7. [7]
  Chunxiu Yu , Zelin Wu , Hongle Shi , Lingyun Gu , Kexin Chen , Chuan-Shu He , Yang Liu , Heng Zhang , Peng Zhou , Zhaokun Xiong , Bo Lai . Insights into the electron transfer mechanisms of peroxydisulfate activation by modified metal-free acetylene black for degradation of sulfisoxazole. Chinese Chemical Letters, 2024, 35(8): 109334-. doi: 10.1016/j.cclet.2023.109334
8. [8]
  Haitao Yin , Liang Meng , Li Li , Jiamu Xiao , Longrui Liang , Nannan Huang , Yansong Shi , Angang Zhao , Jingwen Hou . Polydopamine-modified biochar supported polylactic acid and zero-valent iron affects the functional microbial community structure for 1,1,1-trichloroethane removal in simulated groundwater. Chinese Chemical Letters, 2025, 36(1): 110313-. doi: 10.1016/j.cclet.2024.110313
9. [9]
  Ning DING , Siyu WANG , Shihua YU , Pengcheng XU , Dandan HAN , Dexin SHI , Chao ZHANG . Crystalline and amorphous metal sulfide composite electrode materials with long cycle life: Preparation and performance of hybrid capacitors. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1784-1794. doi: 10.11862/CJIC.20240146
10. [10]
  Yue Xu , Qian Zhang , Qizhao Li , Yongshu Xie . Structures and aromaticity of hexaphyrins(2.1.2.1.2.1) and their metal complexes. Chinese Chemical Letters, 2026, 37(8): 112642-. doi: 10.1016/j.cclet.2026.112642
11. [11]
  Qiao Song , Xue Peng , Zhouyu Wang , Leyong Wang . Iron-catalyzed C–H activation: A sustainable approach to efficient organic synthesis. Chinese Chemical Letters, 2025, 36(5): 110869-. doi: 10.1016/j.cclet.2025.110869
12. [12]
  Haoying ZHAI , Lanzong WEN , Wenjie LIAO , Qin LI , Wenjun ZHOU , Kun CAO . Metal-organic framework-derived sulfur-doped iron-cobalt tannate nanorods for efficient oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1037-1048. doi: 10.11862/CJIC.20240320
13. [13]
  Jianju Li , Xinwei Chen , Yang Yu , Hao Ma , Xinhui Xia , Zixuan Zhao , Junqiu Jiang , Qingliang Zhao , Yingzi Lin , Liangliang Wei . Insights into bioavailable heavy metal impact driven by sludge application on soil nitrification: Toxicity thresholds and influential factors. Chinese Chemical Letters, 2025, 36(7): 110410-. doi: 10.1016/j.cclet.2024.110410
14. [14]
  Li Lin , Song-Lin Tian , Zhen-Yu Hu , Yu Zhang , Li-Min Chang , Jia-Jun Wang , Wan-Qiang Liu , Qing-Shuang Wang , Fang Wang . Molecular crowding electrolytes for stabilizing Zn metal anode in rechargeable aqueous batteries. Chinese Chemical Letters, 2024, 35(7): 109802-. doi: 10.1016/j.cclet.2024.109802
15. [15]
  Ruonan Guo , Heng Zhang , Changsheng Guo , Ningqing Lv , Beidou Xi , Jian Xu . Degradation of neonicotinoids with different molecular structures in heterogeneous peroxymonosulfate activation system through different oxidation pathways. Chinese Chemical Letters, 2024, 35(9): 109413-. doi: 10.1016/j.cclet.2023.109413
16. [16]
  Xue-Lu Ma , Jun-Bo Lu , Yuan Zhang , Ya-Fei Jiang , Jun Li . Dinitrogen fixation on transition metal complexes with flexible axial bonding. Chinese Journal of Structural Chemistry, 2026, 45(3): 100831-100831. doi: 10.1016/j.cjsc.2025.100831
17. [17]
  Zhihui ZONG , Zijie ZHAO , Lei HUANG , Zhicheng PAN , Shan WANG , Lili LIANG , Huaqing LIU , Enli ZHANG . Synthesis, crystal structures, and antitumor activity of two metal complexes of imidazolyl acylhydrazones. Chinese Journal of Inorganic Chemistry, 2026, 42(5): 1048-1062. doi: 10.11862/CJIC.20250330
18. [18]
  Rui Wang , He Qi , Haijiao Zheng , Qiong Jia . Light/pH dual-responsive magnetic metal-organic frameworks composites for phosphorylated peptide enrichment. Chinese Chemical Letters, 2024, 35(7): 109215-. doi: 10.1016/j.cclet.2023.109215
19. [19]
  Jiao Wang , Shuang-Yan Lang , Zhen-Zhen Shen , Gui-Xian Liu , Rui Wen . In situ nanoscale insights into the interfacial degradation of Zn metal anodes. Chinese Chemical Letters, 2025, 36(8): 110308-. doi: 10.1016/j.cclet.2024.110308
20. [20]
  Qiongqiong Wan , Zhourui Zhang , Mengmeng Zhao , Xianqin Ruan , Yanhong Hao , Jiajun Deng , Yunlang She , Minglei Yang , Yongxiang Song , Feng Jin , Ailin Wei , Sheng Zhong , Jie Zheng , Dong Xie , Suming Chen . Efficient diagnosis of benign and malignant pulmonary nodules based on Nano-zero-valent iron enhanced serum metabolic fingerprinting. Chinese Chemical Letters, 2025, 36(10): 110794-. doi: 10.1016/j.cclet.2024.110794

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(17)
HTML views(0)

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