在此，我们证明了通过简便的热解法合成的氟掺杂碳纳米管（F-CNTs），能够在超低PMS用量（0.11 mM）下，通过非自由基途径高效降解4-氯苯酚。机理研究与理论计算相结合表明，半离子态的C-F基团具有双重功能：既增强了相邻碳原子的亲电性，又促进了与PMS分子之间的氢键相互作用（C-F···H-O-OSO3）。这种协同效应促进了PMS的吸附，增强了-O-O-键的极化，并稳定了表面结合的F-CNT-PMS*复合物，从而显著提高了氧化效率。本研究阐明了氟诱导的电子效应和界面效应在促进非自由基PMS活化中的关键作用，为可持续水净化领域的高级碳催化剂提供了战略性设计原则。
Fig. 1. Synthesis and characterization of F-CNTs. (a) Schematic for the synthesis of F-CNTs: (b) XRD patterns. (c) Raman spectra, and (d) TEM image of F-CNTs and the corresponding C、O and F elemental mapping images; (e) the deconvolution F 1 s XPS spectrum of F-CNTs.
Fig. 2. Fenton-like activities of CNTs and F-CNTs for LC-PMS activation: (a) Correlation between PMS utilization and 4-CP removal efficiency. (b) The degradation profiles of 4-CP in (F-)CNTs/LC-PMS system; (c) comparison of the specific activity (kobs) of the catalysts in (F-)CNTs/LC-PMS and comparison of PMS consumption. (d) Comparison of the reaction kinetics (kobs, organic/CPMS) normalized to PMS concentration (mM) for organic pollutants degradation in recently reported heterogeneous PMS-based AOPs. Reaction conditions: [4-CP]0 = 10 mg L−1, [catalyst] = 0.2 g L−1, [PMS/PDS]0 = 0.11 mM, pHinitial = 6.8, and T = 25 °C.
Fig. 3. Identification of generated ROS and formation of hydrogen bond(C-F···H-O-OSO3) between F-CNTs and PMS: (a) Effect of scavengers on 4-CP degradation in F-CNTs/LC-PMS system; (b) The comparison of BA degradation in catalyst/LC-PMS systems. (c) EPR spectra in (F-)CNTs/LC-PMS systems. (d) In-situ Raman spectra of F-CNTs/LC-PMS; (e) The contribution of ROS for 4-CP removal in CNTs/LC-PMS and F-CNTs/LC-PMS systems. (f) F 1 s XPS spectra of F-CNTs, F-CNTs/PMS and F-CNTs/PMS/4-CP. (g) Effect of D2O on the Raman peak of PMS*. (h) Effect of D2O on PMS decomposition in F-CNTs/LC-PMS system. Reaction conditions: [4-CP]0 = 10 mg L−1, [FFA]0 = 11 mM, [MeOH]0 = 50 mM, [TBA]0 = 50 mM, [PBQ]0 = 0.55 mM, [L-HIS]0 = 1.1 mM, [KI]0 = 1.98 mM, [catalyst] = 0.2 g L−1, [PMS]0 = 0.11 mM, pH0 = 6.8, and T = 25 °C.
Fig. 4. Hydrogen-bond-induced enhancement of PMS* reactivity: (a) Correlation between PMS concentration (CPMS) and kobs,4-CP values of F-CNTs and CNTs; K is the slope of the linear relationship between kobs,4-CP and CPMS. (b) Relationship between kobs,PMS and b values of F-CNTs (or CNTs)/LC-PMS systems; b is the slope obtained by fitting log(iₚ) to log(v). (c) The linear correlation between positive potential shift (ΔE) and kobs,PMS values of F-CNTs (or CNTs)/LC-PMS systems; PPMS* is the absolute slope of this correlation. (d) Summarization of K, the intensity of Raman adsorption peaks of PMS*(IPMS*), b0, and PPMS*.
Fig. 5. Theoretical calculation of PMS adsorption and activation on CNTs and F-CNTs catalysts: (a) PMS adsorption energy for F-CNTs and CNTs. (b) Free energy changes against reaction pathways of PMS activation catalyzed by CNTs and F-CNTs for 4-CP oxidation. (c) (d) The charge density differences of CNTs-PMS*-C6H5OCl and F-CNTs-PMS*-C6H5OCl; The cyan and light yellow iso-surfaces depict electron depletion and accumulation; (e) Schematic illustration for F-CNTs (or CNTs) -based LC-PMS activation mechanism.本研究为增强低浓度PMS（0.11 mM）的活化效果以控制水污染提供了一种有效策略。通过NH₄F的低温热解创新制备的氟掺杂碳纳米管（0.7 at% F），通过与PMS形成氢键，加速了电子转移路径，从而实现了多种微污染物的快速去除。与原始碳纳米管相比，氟掺杂碳纳米管（F-CNTs）的芬顿类活性提高了30.8倍。氟掺杂通过引入半离子性C-F位点优化了碳纳米管的电子结构，从而促进了PMS的吸附。这些位点作为强氢键受体，形成了 C-F···H-O-OSO3 相互作用，极化了 PMS 的 O-O 键，从而使 F-CNTs-PMS* 的氧化能力相对于 CNTs-PMS* 提高了 6.7 倍。这显著加速了与有机污染物的电子转移，实现了快速的水净化。此外，F-CNTs/LC-PMS体系展现出优异的解毒效率、TOC去除能力和环境耐受性。连续流实验进一步证实了其卓越的长期运行稳定性，凸显了其强大的应用潜力。总体而言，本研究提出了一种基于LC-PMS的芬顿类体系，为快速高效处理有机废水提供了一种可行方案。
Jingwen Lv, Shuai Wang, Jie Miao, Chao Xu, Qun Li, Haiyong Yao, Yongjun Zhang, Ran Ran, Xixi Wang, Mingce Long, Wei Zhou, Fluorine-doped CNTs for boosted low-concentration peroxymonosulfate activation via enabling strong H-bonding interaction, Applied Catalysis B: Environment and Energy, 2026, https://doi.org/10.1016/j.apcatb.2026.126467
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