基于金属-多酚配位凝胶的油水分离膜仿生构筑与性能研究

Membrane separation has become the key technology for the treatment of industrial oily wastewater due to the characteristics of green, low-carbon and effective. The construction of high-performance oil/water separation membranes has been one of the research focuses in this field. The commonly utilized oil/water separation membranes exhibit the problems of easy-fouling and low-efficiency in selective separation, and thus largely restricting the further improvement of membrane application performance. Therefore, inspired by the metal-protein coordinate structures of mussel byssus, this project is proposed to construct antifouling and high-efficient oil/water separation membrane based on metal-phenolic coordination gels with multiscale structures and multiple interactions. First, based on the metal-phenolic coordination chemistry, coordination gel membranes with highly interconnected channels are constructed, and both the mechanisms of pore structure manipulation and the kinetics of gelation are explored. On the basis of the construction method of coordination gel membranes, highly hydrophilic functional groups are in situ incorporated into the gel network to construct antifouling coordination gel membranes. Both the manipulation mechanisms of surface physico-chemical structures and the effects of membrane structure on surface/interface microenvironment modulation are explored. Employing oil-in-water emulsion as a separation system, the structure-property relationships between membrane structures and oil/water separation performance are explored. High-efficiency oil/water separation can be realized through optimizing the antifouling properties of membrane and enhancing the selective mass-transfer of separation of membrane. It is expected that the achievement from this project will provide references for the design and preparation of high-performance oil/water separation membranes.

膜分离以其绿色、高效、低碳的特点已成为含油污水处理的关键技术，构筑高性能油水分离膜则一直是本领域的研究热点。目前传统油水分离膜普遍存在易污染、选择性分离效率低等问题，很大程度上限制了膜应用性能的提升。为此，本项目受贻贝足丝金属-蛋白配位结构启发，提出以金属-多酚配位凝胶多级结构、多重相互作用为基础仿生构筑抗污染高效油水分离膜的新思路。首先基于金属-多酚配位化学构筑具高连通孔道结构的金属-多酚配位凝胶膜，研究凝胶动力学，探索膜孔道理化结构调控机制；在所建立配位凝胶膜构筑方法基础上，将强亲水基团原位引入凝胶网络构筑抗污染配位凝胶膜，探索膜表面理化结构调控机制，研究膜表面及孔道结构对膜表/界面微环境的调控规律；以水包油型乳化液为分离体系，探索膜结构与膜油水分离性能的构效关系，优化膜抗污染性能、强化膜油水选择性传质过程，实现高效油水分离。期望通过本项目的开展为高性能油水分离膜的设计制备提供参考。

石油与化学工业的发展致使含油污水总量与日俱增，其来源广泛、成分复杂、危害性大，严重威胁我国水环境安全性与可持续发展。发展绿色、高效、低碳的膜法含油污水处理技术，契合含油污水减排和水体油污治理的国家需求。油水分离膜是推动膜技术在含油污水处理中应用的核心材料，设计与创制高性能油水分离膜，契合新型功能材料科技创新的国家需求。本项目受贻贝足丝金属-蛋白配位结构启发，基于金属-多酚配位凝胶的设计与构筑，利用金属-多酚配位凝胶多级结构、多重相互作用的特点，结合相转化和界面组装等方法，制备了可用于油水分离的高性能膜材料。本工作围绕金属-多酚配位凝胶的油水分离膜的仿生构筑方法及其分离性能，研究了不同金属和多酚配比对金属-多酚凝胶化过程的影响，并基于不同金属-多酚凝胶的凝胶化过程的差异性，建立了系列金属-多酚配位凝胶膜的制备方法，探索了金属-多酚配位体系组成、制备条件对膜孔道结构及膜表面结构的调控规律；进一步地基于共凝胶/共组装方法，将亲水性高分子、纳米材料锚定于金属-多酚配位网络中，探明了不同共组装材料对膜表面结构及孔道结构的调控规律；基于所获得系列金属-多酚配位凝胶膜，研究了膜表面结构对膜抗污染性能的影响规律，研究了膜孔道结构对膜水渗透性性能的影响规律，研究了膜表面微纳结构对油水两相在膜表面的选择浸润行为的影响规律，初步形成了膜抗污染性能及油水选择性传质过程的优化与强化策略。本项目创新并拓展了高性能油水分离膜的设计制备与结构调控方法，开发了系类新型金属-多酚配位凝胶膜，实现了油水分离过程的高通量、高效率、抗污染、自清洁，为高效油水分离及含油污水处理提供了新材料和新思路。通过本课题3年的研究共发表负责人作为第一作者或通讯作者SCI论文9篇，获得负责人为第一发明人授权中国发明专利2项。