无机材料学报

• 研究论文 •    

等离子辅助球磨制备煤基稀土催化剂及其对盐酸四环素降解性能

南天翔1,2, 王立昇1, 郭立童1,2, 吴震1, 陶雪钰1, 范贺良1, 郑明1, 冯培忠1   

  1. 中国矿业大学 1.材料与物理学院; 2.矿产资源废弃物循环利用研究中心, 徐州 221116
  • 收稿日期:2026-01-31 修回日期:2026-04-29
  • 作者简介:南天翔(1994-), 男, 博士, 副教授. E-mail: tianxiang.nan@cumt.edu.cn
  • 基金资助:
    国家自然科学基金(52504386, 52474446)

Preparation of Coal-based Rare Earth Catalysts via Plasma-assisted Ball Milling and Performance in the Degradation of Tetracycline Hydrochloride

NAN Tianxiang1,2, WANG Lisheng1, GUO Litong1,2, WU Zhen1, TAO Xueyu1, FAN Heliang1, ZHENG Ming1, FENG Peizhong1   

  1. 1. School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, China;
    2. Center of Mineral Resource Waste Recycling, China University of Mining and Technology, Xuzhou, 221116, China
  • Received:2026-01-31 Revised:2026-04-29
  • About author:NAN Tianxiang (1994-), male, PhD, associate professor. E-mail: tianxiang.nan@cumt.edu.cn
  • Supported by:
    National Natural Science Foundation of China (52504386, 52474446)

摘要: 有机污染废水的高效处理对水环境安全和实现资源可持续发展具有重要意义。目前, 基于过一硫酸盐(PMS)的高级氧化技术虽在降解有机物方面展示出独特优势, 但开发兼具高活性、稳定性与低成本的实用型催化剂仍是该领域面临的主要挑战。本研究采用基于等离子辅助球磨的制备技术合成了煤基稀土-过渡金属多组分催化剂(Vm@PC-FeCoNiSm), 并将其应用于PMS体系降解有机污染物盐酸四环素(TC)。结果表明, 所制备的催化剂具有均匀的微棒状形貌和微‑介孔复合结构, 比表面积达789.2 m2/g。在PMS 2.0 mmol/L、催化剂0.10 g/L条件下, Vm@PC-FeCoNiSm可在30 min内降解96.3%的TC, 其效率显著优于未经等离子处理的对比样品。经过五次循环使用后, 降解效率仍保持在91%以上, 且在实际水体中仍能稳定发挥降解性能。该降解过程由自由基(O2•-、•OH、SO4•-)与非自由基(1O2)共同驱动, 其中O2•-1O2起主导作用, 稀土元素Sm与过渡金属间的电子协同效应是提升PMS活化效率与生成高活性物种的关键。本研究不仅为复杂有机废水的深度处理提供了高性能新材料, 也为煤基碳材料与稀土元素在环境催化中的高值化应用提供了新策略与理论依据。

关键词: 煤基稀土催化剂, 等离子辅助球磨, 盐酸四环素, 降解性能

Abstract: The efficient treatment of organic pollutant-containing wastewater is of great significance for water environmental safety and sustainable resource development. Although peroxymonosulfate (PMS)-based advanced oxidation processes have demonstrated unique advantages in the degradation of organic pollutants, the development of practical catalysts that combine high activity, stability, and low cost remains a major challenge in this field. In this study, a coal-based rare earth-transition metal multicomponent catalyst (Vm@PC-FeCoNiSm) was synthesized via plasma-assisted ball milling and applied in a PMS activation system for organic pollutant tetracycline hydrochloride (TC) degradation. The results show that the as-prepared catalyst exhibits a uniform microrod morphology with a micro-mesoporous composite structure and a high specific surface area of 789.2 m2/g. Under the conditions of 2.0 mmol/L PMS and 0.10 g/L catalyst, Vm@PC-FeCoNiSm achieves 96.3% degradation of TC within 30 min, which is significantly higher than that of the sample prepared without plasma treatment. After five consecutive cycles, the degradation efficiency remains above 91%, and the catalyst maintains stable degradation performance in real water matrices. The degradation process is driven by both radical (O2•-, •OH, SO4•-) and non-radical (1O2) pathways, with O2•- and 1O2 playing dominant roles. The electronic synergistic effect between the rare earth element Sm and the transition metals is critical for enhancing PMS activation efficiency and generating highly reactive species. This study not only provides a high-performance material for the advanced treatment of complex organic wastewater, but also offers a new strategy and theoretical basis for the high-value utilization of coal-based carbon materials and rare earth elements in environmental catalysis.

Key words: coal-based rare earth catalyst, plasma-assisted ball milling, tetracycline hydrochloride, degradation performance

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