Citation: Xiao Tang, Yi Chen, Jing Wang, Xiaoqin Su, Yuting Xu, Rui Peng, Chenglong Yu, Yu Hou, Zhou Cao, Yue Gao, Yong Zhai, Shengyan Pu. The key to unlocking passivated nZVI: Molecular structure-driven activation effect of low-molecular-weight organic acids[J]. Chinese Chemical Letters, ;2026, 37(11): 112674. doi: 10.1016/j.cclet.2026.112674 shu

The key to unlocking passivated nZVI: Molecular structure-driven activation effect of low-molecular-weight organic acids

Xiao Tang ^{a, 1} ,
Yi Chen ^{a, b, 1,} ,
Jing Wang ^a ,
Xiaoqin Su ^a ,
Yuting Xu ^a ,
Rui Peng ^a ,
Chenglong Yu ^{a, b} ,
Yu Hou ^{a, b} ,
Zhou Cao ^{a, b} ,
Yue Gao ^c ,
Yong Zhai ^c ,
Shengyan Pu ^{b, d, *,}

a.
College of Ecology and Environment, Chengdu University of Technology, Chengdu 610059, China
b.
State Key Laboratory of Geohazard Prevention and Geoenvironment Protection, Chengdu University of Technology, Chengdu 610059, China
c.
China Kunlun Contracting & Engineering Corporation, Beijing 100037, China
d.
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China

chenyicdut@163.com

pushengyan13@cdut.edu.cn

Received Date: 14 October 2025
Revised Date: 11 March 2026
Accepted Date: 24 March 2026
Available Online: 24 March 2026

Figures(5)

The passivation of nanoscale zero-valent iron (nZVI) limits its long-term effectiveness in groundwater remediation. While low-molecular-weight organic acids (LMWOAs) can mitigate this issue, how their molecular structures reactivate passivated nZVI (P-ZVI) and regulate its reactivity is not yet fully understood. This study systematically investigated the activation behaviors of eight different LMWOAs on various nZVI systems through material characterization, solution chemistry modeling, and density functional theory (DFT) calculations. Results demonstrate that multi-carboxyl LMWOAs effectively achieve high-efficiency reactivation by synergistically dissolving the passivation layer via proton-ligand interactions, combined with the Fe(Ⅱ)/Fe(Ⅲ) cycle driven by strong complexation stabilization and interfacial electron transfer. This effect remains significant in the presence of pollutants. In contrast, mono-carboxylic acids primarily rely on proton etching, resulting in limited efficiency. Ascorbic acid, with its strong electron transfer capability, shifts the reaction pathway from ^•OH radical-dominated degradation to ligand-to-metal charge transfer, highlighting the multiple activation effects of LMWOAs on P-ZVI. Finally, this study deciphered the three-level “molecular structure–fundamental property–macroscopic performance” structure-activity relationship through multiple linear regression, deciphering the intrinsic mechanisms of how LMWOAs regulate nZVI reactivity. This provides a theoretical basis for the targeted application of LMWOAs in groundwater remediation and the sustainable performance enhancement of nZVI.
1. [1]
  Y. Zhao, J. Song, K. Cheng, et al., Land. Degrad Dev. 35 (2024) 2700–2715. doi: 10.1002/ldr.5103
2. [2]
  A. Galdames, L. Ruiz-rubio, M. Orueta, et al., Int. J. Environ. Res. Public Health. 17 (2020) 5817. doi: 10.3390/ijerph17165817
3. [3]
  Q. Zhou, Y. Li, H. Yang, et al., J. Environ. Sci. 90 (2020) 385–394. doi: 10.1016/j.jes.2019.12.003
4. [4]
  Y. Sun, M. Gu, S. Lyu, et al., J. Hazard. Mater. 392 (2020) 122328. doi: 10.1016/j.jhazmat.2020.122328
5. [5]
  Y. Dai, L. Duan, W. Du, et al., Chemosphere 290 (2022) 133372. doi: 10.1016/j.chemosphere.2021.133372
6. [6]
  W. Wang, P. Zhao, Y. Hu, et al., J. Clean. Prod. 262 (2020) 121341. doi: 10.1016/j.jclepro.2020.121341
7. [7]
  Q. Chen, M. Zhou, Y. Pan, et al., Processes 11 (2023) 620. doi: 10.3390/pr11020620
8. [8]
  A.A.H. Falsal, A.H. Sulaymon, Q.M. Khaliefa, Int. J. Environ. Sci. Tech. 15 (2018) 1123–1138. doi: 10.1007/s13762-017-1466-0
9. [9]
  B. Zhang, L. Zhou, C. Xue, et al., J. Hazard. Mater. 480 (2024) 135851. doi: 10.1016/j.jhazmat.2024.135851
10. [10]
  C.P. Tso, Y.H. Shih, J. Environ. Manage. 206 (2018) 817–825. doi: 10.1016/j.jenvman.2017.11.070
11. [11]
  X. Hou, H. Ma, M. Zhao, et al., Chin. Chem. Lett. 36 (2025) 110332. doi: 10.1016/j.cclet.2024.110332
12. [12]
  Z. Lou, L. Song, X. Zhang, et al., Chem. Eng. J. 507 (2025) 160770. doi: 10.1016/j.cej.2025.160770
13. [13]
  S. Wu, S. Deng, Z. Ma, et al., Chemosphere 287 (2022) 132421. doi: 10.1016/j.chemosphere.2021.132421
14. [14]
  J. Lan, L. Qiu, X. Cai, et al., Sep. Purif. Tech. 331 (2024) 125966. doi: 10.1016/j.seppur.2023.125966
15. [15]
  L. Yang, Y. Deng, D. Gong, et al., Environ. Sci. Pollut. Res. 28 (2021) 9582–9597. doi: 10.1007/s11356-020-11405-8
16. [16]
  K. Zhu, S. Ma, N. Chen, et al., J. Hazard. Mater. 464 (2024) 132960. doi: 10.1016/j.jhazmat.2023.132960
17. [17]
  J. Liang, P. Zhen, L. Liu, et al., Water Res. 265 (2024) 122221. doi: 10.1016/j.watres.2024.122221
18. [18]
  K. Kim, W. Choi, Environ. Sci. Tech. 45 (2011) 2202–2208. doi: 10.1021/es103513u
19. [19]
  M.N. Le, M.S. Lee, J. Min. Metall. Sect. B-Met. 56 (2020) 127–133. doi: 10.2298/jmmb190613055l
20. [20]
  E.T. Kefalas, M. Dakanali, P. Panagiotidis, et al., Inorg. Chem. 44 (2005) 4818–4828. doi: 10.1021/ic050286e
21. [21]
  K. Plessl, A. Russ, D. Vollprecht, Int. J. Environ. Sci. Tech. 20 (2023) 6913–6928. doi: 10.1007/s13762-022-04536-7
22. [22]
  S. Yang, A. Liu, J. Liu, et al., Acta Chim. Sin. 80 (2022) 1536–1554. doi: 10.6023/a22080345
23. [23]
  M. Liao, S. Zhao, K. Wei, et al., Appl. Catal. B: Environ. 330 (2023) 122619. doi: 10.1016/j.apcatb.2023.122619
24. [24]
  L. Jiang, J. Chen, L.X. You, et al., Front. Environ. Sci. 12 (2024) 1429684. doi: 10.3389/fenvs.2024.1429684
25. [25]
  E. Amiruddin, A. Awaluddin, M. Rianna, et al., J. Phys. Conf. Ser. 2733 (2024) 012026. doi: 10.1088/1742-6596/2733/1/012026
26. [26]
  C. Hu, C. Gu, M. Guo, et al., Int. J. Energy Res. 46 (2022) 12378–12390. doi: 10.1002/er.8004
27. [27]
  Z. Yang, X. Ma, C. Shan, et al., J. Hazard. Mater. 368 (2019) 698–704. doi: 10.1016/j.jhazmat.2019.01.105
28. [28]
  Y. Li, H. Liu, X. Li, et al., Water Air Soil Pollut 235 (2024) 181. doi: 10.1007/s11270-024-06987-9
29. [29]
  Z. Wang, P.A. Peng, W. Huang, J. Hazard. Mater. 166 (2009) 992–997. doi: 10.1016/j.jhazmat.2008.11.106
30. [30]
  A. Mikaia, J. Phys. Chem. Ref. Data 51 (2022) 031501. doi: 10.1063/5.0091956
31. [31]
  K. Huang, Y. Xu, W. Lu, et al., Appl. Biochem. Biotechnol. 183 (2017) 1426–1438. doi: 10.1007/s12010-017-2509-1
32. [32]
  M. Vitkova, M. Komarek, V. Tejnecky, et al., J. Hazard. Mater. 293 (2015) 7–14. doi: 10.1016/j.jhazmat.2015.03.033
33. [33]
  X. Chai, X. Qin, X. Gu, et al., Water Air Soil Pollut. 234 (2023) 617. doi: 10.1007/s11270-023-06606-z
34. [34]
  O. Eljamal, R. Mokete, N. Matsunaga, et al., J. Environ. Chem. Eng. 6 (2018) 6207–6220. doi: 10.1016/j.jece.2018.09.012
35. [35]
  H. Wu, Z. Chen, F. Sheng, et al., Sci. Total Environ. 796 (2021) 148923. doi: 10.1016/j.scitotenv.2021.148923
36. [36]
  Z. Zhou, D. Wu, H. Wu, et al., Chemosphere 341 (2023) 139926. doi: 10.1016/j.chemosphere.2023.139926
37. [37]
  S. Yang, W. Yu, B. Du, et al., Chem. Eng. J. 421 (2021) 129967. doi: 10.1016/j.cej.2021.129967
38. [38]
  H. Chen, V.H. Grassian, Environ. Sci. Tech. 47 (2013) 10312–10321. doi: 10.1021/es401285s
39. [39]
  J. Cao, Z. Xiong, B. Lai, Chem. Eng. J. 343 (2018) 492–499. doi: 10.1016/j.cej.2018.03.036
40. [40]
  V. Sladkov, J. Roques, J. Photochem. Photobiol. A: Chem. 322 (2016) 10–15.
41. [41]
  F. Fournier, C. Afonso, A.E. Fagin, et al., J. Am. Soc. Mass Spectrom. 19 (2008) 1887–1896. doi: 10.1016/j.jasms.2008.07.022
42. [42]
  J. Wu, J. Zou, S. Li, et al., Sep. Purif. Technol. 330 (2024) 125382. doi: 10.1016/j.seppur.2023.125382
43. [43]
  X. Min, X. Fan, J. Liu, R. Soc. Open Sci. 5 (2018) 180156. doi: 10.1098/rsos.180156
44. [44]
  Z. Wang, C.C. Ainsworth, D.M. Friedrich, et al., Geochim. Cosmochim. Acta 64 (2000) 1159–1172. doi: 10.1016/S0016-7037(99)00360-9
45. [45]
  D. Jacewicz, A. Chylewska, A. Dabrowska, et al., Z. Anorg. Allg. Chem. 634 (2008) 137–141. doi: 10.1002/zaac.200700344
46. [46]
  Z. Li, M.H. Matus, H.A. Velazquez, et al., Int. J. Mass Spectrom. 265 (2007) 213–223. doi: 10.1016/j.ijms.2007.02.009
47. [47]
  Y. Han, W. Yan, Environ. Sci. Tech. 50 (2016) 12992–13001. doi: 10.1021/acs.est.6b03997
48. [48]
  J. Majzlan, K.D. Grevel, A. Navrotsky, Am. Mineral. 88 (2003) 855–859. doi: 10.2138/am-2003-5-614
49. [49]
  W. Kang, S. Li, C. Wang, et al., Mater. Res. Express. 8 (2021) 045007. doi: 10.1088/2053-1591/abf1a6
50. [50]
  X. Wang, S. Sahoo, J. Gascon, et al., Energy Environ. Sci. 16 (2023) 4388–4403. doi: 10.1039/d3ee01647a
51. [51]
  A. Liu, J. Liu, J. Han, et al., J. Hazard. Mater. 322 (2017) 129–135. doi: 10.1016/j.jhazmat.2015.12.070
52. [52]
  W. Yu, S. Yang, B. Du, et al., J. Hazard. Mater. 396 (2020) 122657. doi: 10.1016/j.jhazmat.2020.122657
53. [53]
  X. Li, W. Fu, R. Guan, et al., Chin. Chem. Lett. 35 (2024) 109625. doi: 10.1016/j.cclet.2024.109625
54. [54]
  H. Zhu, H. Ma, Z. Zhao, et al., J. Hazard. Mater. 486 (2025) 136825. doi: 10.1016/j.jhazmat.2024.136825
55. [55]
  C. Li, K. Zhou, H. He, et al., Int. J. Environ. Res. Public Health 17 (2020) 806. doi: 10.3390/ijerph17030806
56. [56]
  R. Yin, Y. Chen, J. Hu, et al., Appl. Catal. B: Environ. 283 (2021) 119663. doi: 10.1016/j.apcatb.2020.119663
57. [57]
  H. Dai, X. Miao, J. Zhu, et al., Chemosphere 298 (2022) 134240. doi: 10.1016/j.chemosphere.2022.134240
58. [58]
  C. Chang, Q. Wang, Q. Xue, et al., Microchem. J. 173 (2022) 107037. doi: 10.1016/j.microc.2021.107037
59. [59]
  P. Pant, S. Pant, J. Environ. Sci. 22 (2010) 116–126. doi: 10.1016/S1001-0742(09)60082-6
60. [60]
  S. Pu, S. Xue, Z. Yang, et al., Environ. Sci. Pollut. Res. 25 (2018) 17310–17320. doi: 10.1007/s11356-018-1872-y
61. [61]
  Z. Wang, L. Qiu, Y. Huang, et al., Chin. Chem. Lett. 35 (2024) 109195. doi: 10.1016/j.cclet.2023.109195
62. [62]
  K. Efil, I.B. Obot, Prot. Met. Phys. Chem. Surf. 53 (2017) 1139–1149. doi: 10.1134/s2070205118010215
63. [63]
  P. Asselin, A. Schlachter, D. Fortin, et al., Chem. Mater. 34 (2022) 7242–7255. doi: 10.1021/acs.chemmater.2c01105
64. [64]
  K.D. Mcnamara, R.W. Zoellner, Comput. Theor. Chem. 1170 (2019) 112622. doi: 10.1016/j.comptc.2019.112622
65. [65]
  H. Wang, Z. He, Q. Yang, et al., J. Environ. Chem. Eng. 10 (2022) 108365. doi: 10.1016/j.jece.2022.108365
66. [66]
  P. Wang, J. Li, P. An, et al., J. Hydrol. 618 (2023) 129260. doi: 10.1016/j.jhydrol.2023.129260
1. [1]
  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
2. [2]
  Linfeng Li , Bao Wang , Tiantong Zhang , Xinyuan Wang , Dingqiang Feng , Wei Li , Jiangjiexing Wu , Jinli Zhang . Identifying the catalytic active site of durable Ru-based liquid-phase catalyst for acetylene hydrochlorination. Chinese Chemical Letters, 2025, 36(10): 111303-. doi: 10.1016/j.cclet.2025.111303
3. [3]
  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. Chinese Chemical Letters, 2026, 37(8): 112353-. doi: 10.1016/j.cclet.2025.112353
4. [4]
  Lin Cai , Lina Su , Zhiruo Zhou , Jianhua Liu , Li Li , Fengyang Yu , Jiaqi Li , Wenjin Wang , Pengfei Wang , Sihui Zhan . Ho-Engineered electronic structure of LaFeO₃ for enhanced photocatalytic molecular oxygen activation and water purification. Chinese Chemical Letters, 2026, 37(7): 112158-. doi: 10.1016/j.cclet.2025.112158
5. [5]
  Hui Lei , Yingying Jiang , Jiayu Liu , Weifeng Zhang , Fanbo Meng , Jun Mou , Wenyi Liu , Pengcheng Lei , Rui Xiong , Zan Xu , Hang Zhang , Yanjun Wang , Guo-Bo Li , Lingling Yang , Hua-Li Wang . Structure-activity relationship studies of 3,4-disubstitued indole-2-ketone derivatives identify a potent glutaminyl cyclase inhibitor with antitumor activity against breast cancer. Chinese Chemical Letters, 2026, 37(6): 111511-. doi: 10.1016/j.cclet.2025.111511
6. [6]
  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
7. [7]
  Qiao Zhang , Xin Tan , Zihang Liu , Jingyu Ma , Dongqi Cao , Fenfang Li , Shengyi Dong . Optically healable and mechanically tough supramolecular glass from low-molecular-weight compounds. Chinese Chemical Letters, 2025, 36(8): 110660-. doi: 10.1016/j.cclet.2024.110660
8. [8]
  Guannan Zhou , Jiaqi Chen , Li Gong , Houyun Yang , Fazhi Xie , Yang Mu . Nitridated zero-valent iron-driven Fenton-like process for water purification: Performance and mechanism. Chinese Chemical Letters, 2026, 37(11): 112651-. doi: 10.1016/j.cclet.2026.112651
9. [9]
  Hualei Xu , Manman Han , Haiqiang Liu , Liang Qin , Lulu Chen , Hao Hu , Ran Wu , Chenyu Yang , Hua Guo , Jinrong Li , Jinxiang Fu , Qichen Hao , Yijun Zhou , Jinchao Feng , Xiaodong Wang . 4-Nitrocatechol as a novel matrix for low-molecular-weight compounds in situ detection and imaging in biological tissues by MALDI-MSI. Chinese Chemical Letters, 2024, 35(6): 109095-. doi: 10.1016/j.cclet.2023.109095
10. [10]
  Kangren Kong , Zaiqiang Ma , Yu Yin , Zhaoming Liu , Ruikang Tang . Nuclear magnetic resonance-guided Monte Carlo/molecular dynamics structure inference for amorphous solids. Chinese Journal of Structural Chemistry, 2026, 45(3): 100773-100773. doi: 10.1016/j.cjsc.2025.100773
11. [11]
  Jinyan Yang , Ying Chen , Minghan Yu , Lan Zhu , Yilin Wang , Jingsong Chen , Hui Ma , Shengyan Pu . Different natural iron-bearing minerals activated peroxymonosulfate for in-situ chemical oxidation process: Insights into the active Fe sites and activation mechanism. Chinese Chemical Letters, 2026, 37(7): 112210-. doi: 10.1016/j.cclet.2025.112210
12. [12]
  Zhihao HE , Jiafu DING , Yunjie WANG , Xin SU . First-principles study on the structure-property relationship of AlX and InX (X=N, P, As, Sb). Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1007-1019. doi: 10.11862/CJIC.20240390
13. [13]
  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
14. [14]
  Zhen Liu , Xinyi Xu , Jinkai He , Fei Xu , Qian Li . Revealing the synergistic effect of materials composition and pollutants structure on catalytic degradation mechanism in heterogeneous iron-based Fenton-like reactions. Chinese Chemical Letters, 2026, 37(4): 111644-. doi: 10.1016/j.cclet.2025.111644
15. [15]
  Wenliang Wang , Weina Wang , Sufan Wang , Tian Sheng , Tao Zhou , Nan Wei . “Schrödinger Equation – Approximate Models – Core Concepts – Simple Applications”: Constructing a Logical Framework and Knowledge Graph of Atom and Molecule Structures. University Chemistry, 2024, 39(8): 338-343. doi: 10.3866/PKU.DXHX202312084
16. [16]
  Yukun Xing , Xiaoyu Xie , Fangfang Chen . A Sunlit Gift: Vitamin D. University Chemistry, 2024, 39(9): 28-34. doi: 10.12461/PKU.DXHX202402006
17. [17]
  Chunyang Zheng , Shiyu Liu , Nuo Yi , Hong Shang . The Adventures in the Kingdom of Plant Pigments. University Chemistry, 2024, 39(9): 170-176. doi: 10.3866/PKU.DXHX202308085
18. [18]
  Hai-Ling Wang , Zhong-Hong Zhu , Hua-Hong Zou . Structure and assembly mechanism of high-nuclear lanthanide-oxo clusters. Chinese Journal of Structural Chemistry, 2024, 43(9): 100372-100372. doi: 10.1016/j.cjsc.2024.100372
19. [19]
  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
20. [20]
  Yutong Xiong , Ting Meng , Wendi Luo , Bin Tu , Shuai Wang , Qingdao Zeng . Molecular conformational effects on co-assembly systems of low-symmetric carboxylic acids investigated by scanning tunneling microscopy. Chinese Journal of Structural Chemistry, 2025, 44(2): 100511-100511. doi: 10.1016/j.cjsc.2025.100511

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(36)
HTML views(5)

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