铜锰复合陶瓷纳米纤维膜强化类Fenton降解有机污染物

doi:10.19965/j.cnki.iwt.2024-0661

摘要/Abstract

摘要：

为克服传统类Fenton在水处理应用中存在的单一金属氧化物催化活性有限、活性氧物种（ROS）利用率低、粉体催化剂难再生回收等技术瓶颈，以Cu、Mn为核心催化元素，制备了一种铜锰二元复合金属氧化物催化剂Cu_1.5Mn_1.5O₄，并以此构筑了新型铜锰复合催化陶瓷纳米纤维膜，用以强化类Fenton对水中难降解有机污染物的去除。结果表明，Cu_1.5Mn_1.5O₄包含的多价态Cu⁺/Cu²⁺和Mn²⁺/Mn³⁺/Mn⁴⁺可高效催化H₂O₂分解产生多种ROS，实现对水中亚甲基蓝（MB）的高效降解。在中性条件下，0.5 g/L Cu_1.5Mn_1.5O₄可高效催化300 mmol/L H₂O₂在5 min内完全去除10 mg/L MB。新型铜锰复合陶瓷纳米纤维膜既可实现Cu_1.5Mn_1.5O₄在陶瓷膜中的均匀分布，又可通过限域效应缩短类Fenton反应中ROS与有机污染物在膜孔内的传质距离，提高ROS利用率并保障膜出水中有机污染物的高效去除。在40 L/（m²·h）的恒通量膜过滤实验中，催化膜可高效催化50 mmol/L H₂O₂在中性条件下氧化降解10 mg/L MB，膜出水MB去除率接近100%。

关键词: 类Fenton, 铜锰二元金属氧化物, 催化陶瓷纳米纤维膜, 有机污染物

Abstract:

To overcome the technical bottlenecks of traditional Fenton-like process in water treatment applications, such as limited catalytic activity of single metal oxides, low utilization of reactive oxygen species(ROS), and difficult regeneration and recovery of powder catalysts, a copper-manganese binary composite oxide catalyst Cu_1.5Mn_1.5O₄ was prepared with Cu and Mn as the core catalytic elements, and a new copper-manganese composite catalytic ceramic nanofiber membrane was constructed to enhance the removal of refractory organic pollutants in water by Fenton-like process. The results indicated that Cu⁺/Cu²⁺ and Mn²⁺/Mn³⁺/Mn⁴⁺ redox couples contained in Cu_1.5Mn_1.5O₄ could efficiently decompose H₂O₂ into powerful ROS, achieving efficient degradation of methylene blue(MB) in water. Under neutral conditions, 0.5 g/L Cu_1.5Mn_1.5O₄ could efficiently catalyze Fenton-like reaction and achieve 100% removal of 10 mg/L MB at H₂O₂ dosage of 300 mmol/L within 5 minutes. The new copper-manganese composite ceramic nanofiber membrane could not only achieve uniform distribution of Cu_1.5Mn_1.5O₄ in ceramic membrane, but also shorten the mass transfer distance between ROS and organic pollutants in the membrane pores through confinement effect. Therefore, the utilization efficiency of ROS and the removal rate of organic pollutants were significantly improved during catalytic membrane-based Fenton-like system. During the membrane filtration under constant flux of 40 L/(m²·h), the composite membrane could efficiently catalyze the degradation of 10 mg/L MB by 50 mmol/L H₂O₂ under neutral conditions, and the removal rate of MB in effluent was close to 100%.

Key words: Fenton-like process, copper-manganese binary metal oxide, catalytic ceramic nanofiber membrane, organic pollutants

中图分类号:

X703.1

罗航, 唐升引, 邓岳鹏, 王延益, 张锡辉. 铜锰复合陶瓷纳米纤维膜强化类Fenton降解有机污染物[J]. 工业水处理, 2025, 45(9): 123-130.

Hang LUO, Shengyin TANG, Yuepeng DENG, Yanyi WANG, Xihui ZHANG. Copper-manganese composite ceramic nanofiber membrane for enhanced Fenton-like degradation of organic pollutants[J]. Industrial Water Treatment, 2025, 45(9): 123-130.

https://www.iwt.cn/CN/Y2025/V45/I9/123

图/表 6

图1 陶瓷纳米纤维膜催化H₂O₂降解MB的膜过滤实验装置示意

Fig.1 Schematic diagram of membrane filtration experiments for degrading MB by H₂O₂ catalyzed by ceramic nanofiber membrane

图2 10种常见一元金属氧化物催化H₂O₂降解MB的性能

Fig.2 Performance of 10 common monometallic oxide catalysts in H₂O₂-catalyzed degradation of MB

图3 铜锰二元复合金属氧化物的表征

Fig.3 Characterization of copper-manganese binary composite metal oxide

图4 Cu_1.5Mn_1.5O₄催化H₂O₂降解MB的性能

Fig.4 Performance of Cu_1.5Mn_1.5O₄ in H₂O₂-catalyzed degradation of MB

图5 陶瓷纳米纤维膜的形貌结构和元素分布（a~f）及XRD（g）

Fig.5 Morphology， structure and element distribution（a-f）， and XRD（g） of ceramic nanofiber membrane

图6 陶瓷纳米纤维膜的膜通量及其催化H₂O₂降解MB的性能

Fig.6 Membrane flux of ceramic nanofiber membrane and its performance in H₂O₂-catalyzed degradation of MB

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