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Vol. 18 (2026)

Electron Redistribution by Fluorine-Induced Dual Defects in Cu3P Accelerated Charge Transfer Toward High-Performance Electrochemical Chloride Ion Removal

https://doi.org/10.1007/s40820-026-02267-9
Ziqing Zhou
State Key Laboratory of Pollution Control and Resource Reuse, Research Center for Environmental Functional Materials, College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, People’s Republic of China
Yifan Ren
State Key Laboratory of Pollution Control and Resource Reuse, Research Center for Environmental Functional Materials, College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, People’s Republic of China
Fei Yu
College of Oceanography and Ecological Science, Shanghai Ocean University, No 999, Huchenghuan Road, Shanghai 201306, People’s Republic of China
Jie Ma
State Key Laboratory of Pollution Control and Resource Reuse, Research Center for Environmental Functional Materials, College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, People’s Republic of China

Corresponding Author: Jie Ma

jma@tongji.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 412

Abstract

Electrochemical chloride ion removal is essential for clean water and environmental protection, yet its practical application is hindered by the sluggish kinetics, especially using high-mass-loading electrodes. Conventional extrinsic modifications, such as conductive additives or structural design, exhibit constrained effectiveness. Here, we report an intrinsic enhancement strategy through heteroatom doping-induced dual defects engineering, demonstrated by the successful synthesis of fluorine-doped copper(I) phosphide with phosphorus vacancies (F-Cu3PV) via molten salt treatment. Based on density functional theory calculations and experimental results, F doping caused lattice distortion, generating P vacancies to form dual defects. These defects effectively modulated intrinsic electron redistribution, resulting in improved electrical conductivity, enhanced adsorption capability, and reduced chloride ion diffusion energy barriers. Therefore, electron transfer and ion diffusion kinetics were significantly accelerated, leading to superior electrochemical performance. Resultantly, the F-Cu3PV electrode performed exceptional electrochemical chloride ion removal performance with superior areal deionization capacity (3.16 ± 0.02 mg cm−2) and a remarkably rapid areal deionization rate (0.106 ± 0.001 mg cm−2 min−1), as well as outstanding cycling stability (95.65% retention after 70 cycles). This work elucidates electron redistribution via heteroatom doping-induced dual defects as a viable pathway to overcome the intrinsic kinetic bottleneck for high-performance electrochemical chloride ion removal.


Highlights:
1 Heteroatom doping-induced vacancy was achieved by molten salt treatment.
2 The dual defects led to marked electron redistribution, accelerating electron transfer and ion diffusion kinetics.
3 The electrodes with dual defects exhibited superior areal deionization capacity and rate.

Keywords

Fluorine doping Phosphorus vacancy Copper(I) phosphide Electron redistribution Chloride ion removal
Zhou, Ziqing, Yifan Ren, Fei Yu, and Jie Ma. 2026. “Electron Redistribution by Fluorine-Induced Dual Defects in Cu3P Accelerated Charge Transfer Toward High-Performance Electrochemical Chloride Ion Removal”. Nano-Micro Letters 18 (June):412. https://doi.org/10.1007/s40820-026-02267-9.
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References
  1. M. Yuan, H. Liu, F. Ran, Fast-charging cathode materials for lithium & sodium ion batteries. Mater. Today 63, 360–379 (2023). https://doi.org/10.1016/j.mattod.2023.02.007
  2. Q. Li, Y. Zheng, D. Xiao, T. Or, R. Gao et al., Faradaic electrodes open a new era for capacitive deionization. Adv. Sci. 7(22), 2002213 (2020). https://doi.org/10.1002/advs.202002213
  3. B. Tang, Y. Wei, R. Jia, F. Zhang, Y. Tang, Rational design of high-loading electrodes with superior performances toward practical application for energy storage devices. Small 20(15), 2308126 (2024). https://doi.org/10.1002/smll.202308126
  4. H. Sun, J. Zhu, D. Baumann, L. Peng, Y. Xu et al., Hierarchical 3D electrodes for electrochemical energy storage. Nat. Rev. Mater. 4(1), 45–60 (2019). https://doi.org/10.1038/s41578-018-0069-9
  5. R. Chen, H. Tang, P. He, W. Zhang, Y. Dai et al., Interface engineering of biomass-derived carbon used as ultrahigh-energy-density and practical mass-loading supercapacitor electrodes. Adv. Funct. Mater. 33(8), 2212078 (2023). https://doi.org/10.1002/adfm.202212078
  6. T. Liu, Z. Zhou, Y. Guo, D. Guo, G. Liu, Block copolymer derived uniform mesopores enable ultrafast electron and ion transport at high mass loadings. Nat. Commun. 10, 675 (2019). https://doi.org/10.1038/s41467-019-08644-w
  7. Y. Wang, A.S. Mijailovic, T. Ji, E. Cakmak, X. Zhao et al., Promoting electrochemical rates by concurrent ionic-electronic conductivity enhancement in high mass loading cathode electrode. Energy Storage Mater. 71, 103546 (2024). https://doi.org/10.1016/j.ensm.2024.103546
  8. Y. Zhang, Y. Li, J. Chen, J. Zhao, T. Li et al., Directed electrostatic self-assembly of (110)-oriented 2D/2D BiOCl/MXene heterojunctions for high-efficiency capacitive deionization. Sep. Purif. Technol. 394, 137635 (2026). https://doi.org/10.1016/j.seppur.2026.137635
  9. Z. Zhao, M. Sun, W. Chen, Y. Liu, L. Zhang et al., Sandwich, vertical-channeled thick electrodes with high rate and cycle performance. Adv. Funct. Mater. 29(16), 1809196 (2019). https://doi.org/10.1002/adfm.201809196
  10. Z. Ju, X. Zhang, J. Wu, S.T. King, C.-C. Chang et al., Tortuosity engineering for improved charge storage kinetics in high-areal-capacity battery electrodes. “Nano Lett.” 22(16), 6700–6708 (2022). https://doi.org/10.1021/acs.nanolett.2c02100
  11. N. Wang, X. Zhang, Z. Ju, X. Yu, Y. Wang et al., Thickness-independent scalable high-performance Li-S batteries with high areal sulfur loading via electron-enriched carbon framework. Nat. Commun. 12, 4519 (2021). https://doi.org/10.1038/s41467-021-24873-4
  12. Z. Zhou, Y. Ren, F. Yu, J. Ma, Monolithic low-tortuous copper(I) phosphide nanorod arrays for exceptional areal performance in electrochemical chloride ion removal. Nano Energy 137, 110792 (2025). https://doi.org/10.1016/j.nanoen.2025.110792
  13. P. Muhammad, A. Zada, J. Rashid, S. Hanif, Y. Gao et al., Defect engineering in nanocatalysts: from design and synthesis to applications. Adv. Funct. Mater. 34(29), 2314686 (2024). https://doi.org/10.1002/adfm.202314686
  14. C. Wu, X.-L. Shi, L. Wang, W. Lyu, P. Yuan et al., Defect engineering advances thermoelectric materials. “ACS Nano” 18(46), 31660–31712 (2024). https://doi.org/10.1021/acsnano.4c11732
  15. J. Zhao, Y. Zhang, Z. Zhuang, Y. Deng, G. Gao et al., Tailoring d–p orbital hybridization to decipher the essential effects of heteroatom substitution on redox kinetics. Angew. Chem. Int. Ed. 136(33), e202404968 (2024). https://doi.org/10.1002/ange.202404968
  16. Z. Lao, Z. Han, J. Ma, M. Zhang, X. Wu et al., Band structure engineering and orbital orientation control constructing dual active sites for efficient sulfur redox reaction. Adv. Mater. 36(2), 2309024 (2024). https://doi.org/10.1002/adma.202309024
  17. J. Chi, L. Guo, J. Mao, T. Cui, J. Zhu et al., Modulation of electron structure and dehydrogenation kinetics of nickel phosphide for hydrazine-assisted self-powered hydrogen production in seawater. Adv. Funct. Mater. 33(46), 2300625 (2023). https://doi.org/10.1002/adfm.202300625
  18. X. Liu, Q. Yu, X. Qu, X. Wang, J. Chi et al., Manipulating electron redistribution in Ni2P for enhanced alkaline seawater electrolysis. Adv. Mater. 36(1), 2307395 (2024). https://doi.org/10.1002/adma.202307395
  19. Y. Sun, J. Dai, H. Lv, L. Dong, Z. Wang et al., Superhydrophilic V-doped CoP Nanops@Cu3P nanotubes with vacancy and interface engineering for synergistically enhanced electrocatalytic overall water splitting. Adv. Funct. Mater. 35(40), 2505867 (2025). https://doi.org/10.1002/adfm.202505867
  20. K. Xu, Y. Sun, X. Li, Z. Zhao, Y. Zhang et al., Fluorine-induced dual defects in cobalt phosphide nanosheets enhance hydrogen evolution reaction activity. ACS Mater. Lett. 2(7), 736–743 (2020). https://doi.org/10.1021/acsmaterialslett.0c00209
  21. Y. Xue, Q. Zhang, W. Wang, H. Cao, Q. Yang et al., Opening two-dimensional materials for energy conversion and storage: a concept. Adv. Energy Mater. 7(19), 1602684 (2017). https://doi.org/10.1002/aenm.201602684
  22. C. Guan, X. Yue, Q. Xiang, The role of lattice distortion in catalysis: functionality and distinctions from strain. Adv. Mater. 37(30), 2501209 (2025). https://doi.org/10.1002/adma.202501209
  23. J. Tao, L. Xu, C. Pei, Y. Gu, Y. He et al., Catfish effect induced by anion sequential doping for microwave absorption. Adv. Funct. Mater. 33(8), 2211996 (2023). https://doi.org/10.1002/adfm.202211996
  24. T. Kou, T. Smart, B. Yao, I. Chen, D. Thota et al., Theoretical and experimental insight into the effect of nitrogen doping on hydrogen evolution activity of Ni3S2 in alkaline medium. Adv. Energy Mater. 8(19), 1703538 (2018). https://doi.org/10.1002/aenm.201703538
  25. Y. Bo, H. Wang, Y. Lin, T. Yang, R. Ye et al., Altering hydrogenation pathways in photocatalytic nitrogen fixation by tuning local electronic structure of oxygen vacancy with dopant. Angew. Chem. Int. Ed. 60(29), 16085–16092 (2021). https://doi.org/10.1002/anie.202104001
  26. Y. Gao, K. Wang, C. Xu, H. Fang, H. Yu et al., Enhanced electrocatalytic nitrate reduction through phosphorus-vacancy-mediated kinetics in heterogeneous bimetallic phosphide hollow nanotube array. Appl. Catal. B Environ. 330, 122627 (2023). https://doi.org/10.1016/j.apcatb.2023.122627
  27. J. Zhu, J. Chi, T. Cui, L. Guo, S. Wu et al., F doping and P vacancy engineered FeCoP nanosheets for efficient and stable seawater electrolysis at large current density. Appl. Catal. B Environ. 328, 122487 (2023). https://doi.org/10.1016/j.apcatb.2023.122487
  28. Y. Zhang, K. Li, Y. Li, J. Mi, C. Li et al., Charge redistribution of lattice-mismatched Co─Cu3P boosting pH-universal water/seawater hydrogen evolution. Small 20(37), 2400244 (2024). https://doi.org/10.1002/smll.202400244
  29. X. Xu, K. Guo, J. Sun, X. Yu, X. Miao et al., Interface engineering of Mo-doped Ni2P/FexP-V multiheterostructure for efficient dual-pH hydrogen evolution and overall water splitting. Adv. Funct. Mater. 34(33), 2400397 (2024). https://doi.org/10.1002/adfm.202400397
  30. Y. Sun, W. Sun, L. Chen, A. Meng, G. Li et al., Surface reconstruction, doping and vacancy engineering to improve the overall water splitting of CoP nanoarrays. Nano Res. 16(1), 228–238 (2023). https://doi.org/10.1007/s12274-022-4702-y
  31. Y.-N. Zhou, M.-X. Li, S.-Y. Dou, H.-Y. Wang, B. Dong et al., Promoting oxygen evolution by deep reconstruction via dynamic migration of fluorine anions. ACS Appl. Mater. Interfaces 13(29), 34438–34446 (2021). https://doi.org/10.1021/acsami.1c09308
  32. L. Peng, Y. Bai, H. Li, M. Qu, Z. Wang et al., Boosting bidirectional sulfur conversion enabled by introducing boron-doped atoms and phosphorus vacancies in Ni2P for lithium-sulfur batteries. J. Energy Chem. 100, 760–769 (2025). https://doi.org/10.1016/j.jechem.2024.09.027
  33. S. Zhang, X. Liu, C. Liu, S. Luo, L. Wang et al., MoS2 quantum dot growth induced by S vacancies in a ZnIn2S4 monolayer: atomic-level heterostructure for photocatalytic hydrogen production. ACS Nano 12(1), 751–758 (2018). https://doi.org/10.1021/acsnano.7b07974
  34. Z. Ran, C. Shu, Z. Hou, W. Zhang, Y. Yan et al., Modulating electronic structure of honeycomb-like Ni2P/Ni12P5 heterostructure with phosphorus vacancies for highly efficient lithium-oxygen batteries. Chem. Eng. J. 413, 127404 (2021). https://doi.org/10.1016/j.cej.2020.127404
  35. M. He, J. Long, M. Li, R. Zheng, A. Hu et al., Synergy of cobalt vacancies and iron doping in cobalt selenide to promote oxygen electrode reactions in lithium-oxygen batteries. J. Colloid Interface Sci. 612, 171–180 (2022). https://doi.org/10.1016/j.jcis.2021.12.148
  36. R. Zheng, C. Shu, X. Chen, Y. Yan, M. He et al., Unique intermediate adsorption enabled by anion vacancies in metal sulfide embedded MXene nanosheets overcoming kinetic barriers of oxygen electrode reactions in lithium-oxygen batteries. Energy Storage Mater. 40, 41–50 (2021). https://doi.org/10.1016/j.ensm.2021.04.041
  37. L. Jiang, L. Jiang, X. Luo, R. Li, Q. Zhou et al., Iron-Induced vacancy and electronic regulation of nickle phosphides for ampere-level alkaline water/seawater splitting. Chem. Eng. J. 502, 157952 (2024). https://doi.org/10.1016/j.cej.2024.157952
  38. H. Liu, S. Hu, B. Long, H. Dai, Y. Yang et al., In situ unraveling surface reconstruction of Ni-CoP nanowire for excellent alkaline water electrolysis. Energy Environ. Mater. 8(2), e12834 (2025). https://doi.org/10.1002/eem2.12834
  39. S. Ardizzone, G. Fregonara, S. Trasatti, “Inner” and “outer” active surface of RuO2 electrodes. Electrochim. Acta 35(1), 263–267 (1990). https://doi.org/10.1016/0013-4686(90)85068-X
  40. B. Sun, M. Yao, Y. Chen, X. Tang, W. Hu et al., Facile fabrication of flower-like γ-Fe2O3 @PPy from iron rust for high-performing asymmetric supercapacitors. J. Alloys Compd. 922, 166055 (2022). https://doi.org/10.1016/j.jallcom.2022.166055
  41. D. Mondal, M. Kundu, B.K. Paul, D. Bhattacharya, S. Sarkar et al., Rare earth ion-doped α-MnO2 nanorods for an asymmetric supercapacitor. ACS Appl. Nano Mater. 7(5), 4913–4926 (2024). https://doi.org/10.1021/acsanm.3c05666
  42. H.S. Nishad, V. Kotha, P. Sarawade, A.C. Chaskar, S. Mane et al., Exchanging interlayer anions in NiFe-LDHs nanosphere enables superior battery-type storage for high-rate aqueous hybrid supercapacitors. J. Mater. Chem. A 12(16), 9494–9507 (2024). https://doi.org/10.1039/d4ta00299g
  43. H.S. Nishad, S.D. Tejam, S.M. Mane, S.P. Patole, A.V. Biradar et al., Temperature-driven enhancement in pseudocapacitive charge storage of Sn-doped WO3 nanoflowers and its high-performance quasi-solid-state asymmetric supercapacitor. J. Energy Storage 77, 109842 (2024). https://doi.org/10.1016/j.est.2023.109842
  44. Z. Peng, S. Li, Y. Huang, J. Guo, L. Tan et al., Sodium-intercalated manganese oxides for achieving ultra-stable and fast charge storage kinetics in wide-voltage aqueous supercapacitors. Adv. Funct. Mater. 32(46), 2206539 (2022). https://doi.org/10.1002/adfm.202206539
  45. Y. Shi, T. Liu, R. Hu, H. Xu, C. Yang et al., Synergy of W doping and oxygen vacancy engineering on d-band center modulation for enhanced gas sensing performance. J. Mater. Chem. A 12(8), 4770–4781 (2024). https://doi.org/10.1039/d3ta07007g
  46. L. Yang, S. Wang, N. Ma, W. Shi, Z. Fang et al., Modulating binding strength and acidity of benzene-derivative ligands enables efficient and hysteresis-free perovskite/silicon tandem solar cells. Angew. Chem. Int. Ed. 64(21), e202500350 (2025). https://doi.org/10.1002/anie.202500350
  47. M. Liang, N. Liu, X. Zhang, Y. Xiao, J. Yang et al., A reverse-defect-engineering strategy toward high edge-nitrogen-doped nanotube-like carbon for high-capacity and stable sodium ion capture. Adv. Funct. Mater. 32(49), 2209741 (2022). https://doi.org/10.1002/adfm.202209741
  48. B. Wang, K. Qian, X. Jiao, G. Yuan, J. Bai et al., Metal doping and vacancy synergistic induced electron/ion engineering to optimize the redox kinetics of sodium storage: a case study Mo1-xWxSe2. Energy Storage Materials 63, 102998 (2023). https://doi.org/10.1016/j.ensm.2023.102998
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