钴基金属有机框架材料及衍生物层状膜分离降解有机污染物的研究

膜分离技术作为一种高效且低能耗的先进分离技术，无需相变即可实现出色的污染物去除效率。其中，基于二维金属有机框架（2D MOFs）材料的层状膜，以其独特的多孔及层间结构和表面功能性官能团，有望展现出更高的选择渗透性和功能性。此外，其高温衍生材料不仅能够保持原有的二维结构，还有望提高其在实际水环境应用中的稳定性。

尽管如此，目前对2D MOF及其衍生材料膜在水处理应用的研究还处于初级阶段。尚未充分利用MOF的孔径调节特性来优化2D MOF层状膜的选择性分离性能，也缺乏通过高温热解技术提高2D MOF层状膜在催化降解水中有机污染物的应用稳定性的研究。本论文聚焦于Co为金属活性中心的2D Co-MOF材料，专注于高盐染料废水的选择性分离与难降解有机物污染水体的稳定催化处理。具体研究内容如下：

（1）采用对苯二甲酸、萘二甲酸和联苯二甲酸作为有机配体，制备具有不同内部孔径的2D Co-MOF层状膜，以实现高效且选择性的染料回收。相比无孔纳米片膜，Co-MOF层状膜通过精确调节面内孔径，展现出卓越的渗透性和选择性。通过调整配体的长度，实现面内孔径从1.01 × 0.63到1.43 × 0.64 nm²的精确控制。在扩散和压力驱动过滤模式下，Co-MOF层状膜不仅对盐分显示出极佳的选择透过性，同时也实现了对染料分子的高截留率和可调节的水通量。这种出色的渗透性和选择性，归功于Co-MOF纳米片上的平面内孔结构，这些孔结构充当了水和盐分快速透过的“电梯”，而对染料分子则表现出强烈的排斥作用。通过不同pH溶液长期过滤性能测试和Co离子浸出实验，进一步证明了Co-MOF层状膜的稳定性。

（2）为增强Co-MOF层状膜在高级氧化工艺中的稳定性，通过高温热解技术将Co-MOF前驱体转化为包覆Co纳米颗粒并具有层状结构的碳化物材料（Co@C）。通过剥离并有序堆叠纳米片制备Co@C NS（Nanosheet）层状膜，并研究该膜催化过一硫酸盐降解双酚A（BPA）的效率及稳定性。Co@C NS层状膜展现了对BPA的超高去除效率，在1100 L m⁻² h⁻¹ bar⁻¹的超高水通量下实现100%的BPA去除。此高催化效率来源于层间/层内纳米通道的限域效应，增强了原位产生的单线态氧和硫酸根自由基对BPA的去除效率。此外，该膜通过尺寸排斥分离天然有机物（NOM），显著减轻了NOM竞争活性氧基团的影响及对BPA降解的干扰。在稳定性方面，碳层的形成有效阻止了Co离子释放，确保了材料膜的长期结构和催化稳定性。

本论文通过调控Co-MOF纳米片的有机配体长度精确控制膜的孔径，优化了选择性分离效率，并结合高温热解技术提高了催化稳定性，为2D MOF层状膜在功能性分离领域的应用提供了新思路。

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