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铜钴双金属MOF催化膜的制备及其活化过氧乙酸和降解染料性能研究

作者：石玉清¹，²，李贵亮²，³，刘富²，³

单位： 1．宁波大学材料科学与化学工程学院，宁波 315211; 2．中国科学院宁波材料技术与工程研究所，宁波 315201; 3．中国科学院大学宁波材料工程学院，宁波 315201

关键词：过氧乙酸；双金属MOF；高级氧化；催化膜

DOI号： 10.16159/j.cnki.issn1007-8924.2025.04.006

分类号： TB383.2; TQ426; X703

出版年,卷(期):页码： 2025,45(4):53-64

摘要：

本研究针对现有吸附、膜分离等技术在处理有机污染物废水时的局限性，如效率受限、浓缩污染物仍需进一步处理，基于铜钴双金属有机框架（CuCo-MOF）催化膜的高级氧化体系，高效活化绿色氧化剂过氧乙酸（PAA）实现对印染废水中染料分子的快速降解。通过共沉淀法制备纳米片状CuCo-MOF催化剂，并采用真空辅助组装方式制备CuCo-MOF催化膜（CuCo-CM）。以亚甲基蓝分子作为模型分子，在PAA的作用下，在10 min内，CuCo-MOF可实现约95%的亚甲基蓝降解，而CuCo-CM仅需2 min即可达到相同降解效果，显著提高了降解速率。活性氧淬灭实验表明，体系中单线态氧（1O2）是主导降解过程的活性物种，同时高价金属物种[Co（Ⅳ）]对亚甲基蓝的降解亦存在协同贡献。长期稳定性测试显示，CuCo-CM在24 h后仍能维持约80%的降解效率，且通量保持在110 L/(m2·h)以上。所制备的CuCo-CM可有效实现印染废水中有机污染物的降解，表现出优异的催化性能和运行稳定性，有望用于实际废水的深度处理。

This study addresses the limitations of existing technologies such as adsorption and membrane separation in treating organic pollutant wastewater, including restricted efficiency and the need for further treatment of concentrated pollutants. A Cu-Co bimetallic metal-organic framework (CuCo-MOF) catalytic membrane was developed to construct an advanced oxidation system for efficiently activating the green oxidant peracetic acid (PAA) and achieving rapid degradation of dye molecules in textile wastewater. A nanosheet-structured CuCo-MOF catalyst was synthesized via a coprecipitation method, and a CuCo-MOF catalytic membrane (CuCo-CM) was fabricated using vacuum-assisted assembly. Using methylene blue (MB) as a model pollutant, CuCo-MOF achieved approximately 95% degradation within 10 min under PAA activation, while CuCo-CM required only 2 min to reach the same degradation efficiency, significantly enhancing the degradation rate. Reactive oxygen species quenching experiments confirmed that singlet oxygen (1O2) was the dominant reactive species in the system. Additionally, high-valent metal species such as Co(Ⅳ) contributed to methylene blue degradation through a non-radical oxidation pathway. Long-term stability tests showed that CuCo-CM maintained approximately 80% degradation efficiency after 24 hours, with a flux exceeding 110 L/(m2·h). The prepared CuCo-CM effectively degrades organic pollutants in textile wastewater, demonstrating excellent catalytic performance and operational stability, making it a promising candidate for advanced wastewater treatment.

基金项目：

国家自然科学基金项目（52373112）

作者简介：

石玉清（2000-），女，安徽安庆人，硕士研究生，主要从事高级氧化催化膜研究

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