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<p>In this study, a novel composite of derived carbon fiber-supported Mn<sub>3</sub>O<sub>4</sub> nanoparticles (Mn<sub>3</sub>O<sub>4</sub>@DC) was synthesized from waste textiles, followed by characterization and testing. Tetracycline hydrochloride (TCH) was selected as a model pollutant to evaluate the capability of this composite to activate peroxymonosulfate (PMS). Results showed that Mn<sub>3</sub>O<sub>4</sub>@DC effectively activated PMS to degrade TCH, achieving a total removal efficacy of 80.8% within 60&#xa0;min. The degradation efficiency of TCH was significantly enhanced under optimized conditions, which included higher dosages of both the Mn<sub>3</sub>O<sub>4</sub>@DC catalyst and PMS, as well as an acidic pH. The influence of coexisting anions was system-dependent: H<sub>2</sub>PO<sub>4</sub>⁻ and HCO<sub>3</sub>⁻ exerted inhibitory effects, whereas Cl⁻, SO<sub>4</sub><sup>2</sup>⁻, and NO<sub>3</sub>⁻ promoted degradation. The extent of these effects is likely governed by a combination of anion type, concentration, and the reactive species generated. The presence of humic acid (HA) suppressed degradation, attributable to its coordination with manganese active sites and competitive adsorption with TCH. Furthermore, the Mn<sub>3</sub>O<sub>4</sub>@DC catalyst demonstrated strong anti-interference capability in complex water matrices and maintained high catalytic activity over five consecutive reaction cycles, highlighting its satisfactory stability and practical potential. Combined analysis using electron paramagnetic resonance (EPR), quenching experiments, and electrochemical tests confirmed that both superoxide radicals (•O<sub>2</sub>⁻) and direct electron transfer play crucial roles in the Mn<sub>3</sub>O<sub>4</sub>@DC/PMS system. Based on density functional theory (DFT) calculations and Q-TOF–MS analysis, three potential degradation pathways for TCH were proposed. Finally, the ECOSAR program was employed to evaluate the ecotoxicity of TCH and its degradation intermediates toward aquatic organisms (fish, daphnid, and green algae). This study demonstrates that Mn<sub>3</sub>O<sub>4</sub>@DC is a promising, economical, and environmentally benign nanocatalyst for persulfate activation, suggesting its potential for broadening the application of manganese-based carbon catalysts in environmental remediation.</p> Graphical Abstract <p></p>

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Promoting Peroxymonosulfate Activation via Derived Carbon Fiber-Supported Mn3O4: Synergistic Mechanism of Radical and Nonradical Pathways

  • 期刊论文

  • 发表日期：

    2026年2月3日

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  • Xueying Li,
  • Liangliang Yan,
  • Jiahui Niu,
  • Lang Chen,
  • Yuwei Deng,
  • Xuanyuan Pei,
  • Zhenbin Wu,
  • Binghua Jing,
  • Fei Pan

摘要

In this study, a novel composite of derived carbon fiber-supported Mn3O4 nanoparticles (Mn3O4@DC) was synthesized from waste textiles, followed by characterization and testing. Tetracycline hydrochloride (TCH) was selected as a model pollutant to evaluate the capability of this composite to activate peroxymonosulfate (PMS). Results showed that Mn3O4@DC effectively activated PMS to degrade TCH, achieving a total removal efficacy of 80.8% within 60 min. The degradation efficiency of TCH was significantly enhanced under optimized conditions, which included higher dosages of both the Mn3O4@DC catalyst and PMS, as well as an acidic pH. The influence of coexisting anions was system-dependent: H2PO4⁻ and HCO3⁻ exerted inhibitory effects, whereas Cl⁻, SO42⁻, and NO3⁻ promoted degradation. The extent of these effects is likely governed by a combination of anion type, concentration, and the reactive species generated. The presence of humic acid (HA) suppressed degradation, attributable to its coordination with manganese active sites and competitive adsorption with TCH. Furthermore, the Mn3O4@DC catalyst demonstrated strong anti-interference capability in complex water matrices and maintained high catalytic activity over five consecutive reaction cycles, highlighting its satisfactory stability and practical potential. Combined analysis using electron paramagnetic resonance (EPR), quenching experiments, and electrochemical tests confirmed that both superoxide radicals (•O2⁻) and direct electron transfer play crucial roles in the Mn3O4@DC/PMS system. Based on density functional theory (DFT) calculations and Q-TOF–MS analysis, three potential degradation pathways for TCH were proposed. Finally, the ECOSAR program was employed to evaluate the ecotoxicity of TCH and its degradation intermediates toward aquatic organisms (fish, daphnid, and green algae). This study demonstrates that Mn3O4@DC is a promising, economical, and environmentally benign nanocatalyst for persulfate activation, suggesting its potential for broadening the application of manganese-based carbon catalysts in environmental remediation.

Graphical Abstract