亲油/疏油性可光响应切换的碳基分子印迹吸附材料用于油品中噻吩类硫化物的萃取脱除

To resolve the contradiction between dispersibility and solid-liquid separability of extraction adsorbent that designed for oil desulfurization, this project combines the surface imprinting technique and wettability modulation technique. The ordered mesoporous carbon nanospheres with excellent dispersibility and surfactivity will be chose as support material. Several modification methods such as atomic/molecular layer deposition, self-assembly process and liquid-phase polymerization will be adopted to modify the properities of the carbon support. The fabrication of imprinted cavities make the adsorbent has selective recognition ability to the target molecules. Meanwhile, the introduction of photosensitived TiO2 and the fluorine reagent (1H,1H,2H,2H-perflurodecyltrichlorosilane) make the adsorbent has UV responsive oleophobic/philic reversible propertiy. Thus, the bifunctional carbon based molecularly imprinted adsorbent can be acquired. .Through this research project, the affects of photosensitive groups to imprinting cavities can be clarified, the mechanism for specific selectivity of SMIP towards thiophenes can be revealed, the relationship between structure and properties can be elucidated and the adsorption and release cycle of adsorbent can be well understood. Besides, the way to obtain a bifunctional surface with abilities of molecular recognition and oleophobic/philic UV responsive modulate can be paved. Overall, the research will have great contribution to the produce of clean fuel oil and recycle the valuable thiophene compounds at the same time.

用于油品中有机硫化物萃取脱除的吸附剂，在使用时需要具备良好的溶剂分散性而在使用后又需要具备优良的固液分离性能，而现有萃取吸附剂往往难以兼顾这两项性能。针对这一难题，本项目将表面印迹技术同光响应表面浸润性调变技术相结合，选用溶剂分散性和表面活性俱佳的有序介孔碳纳米球作为基质，采用原子/分子层沉积、液相聚合等修饰手段，使其表面逐步功能化，通过印迹孔穴的构建使材料对目标分子具有专一识别性，通过光敏TiO2和低表面能氟试剂（1H,1H,2H,2H-全氟癸基三氯硅烷）的引入实现材料表面亲油/疏油性紫外光响应切换，由此获得具有识别性与光响应性的双功能碳基印迹萃取吸附材料。.通过上述研究，可以阐明光响应基团对印迹孔穴的影响规律，揭示印迹材料对目标分子的识别、吸附、释放过程机制，获得分子识别与亲油/疏油性可切换的双功能层构建技术，实现深度脱硫的同时富集回收高值噻吩类硫化物，具有良好理论价值和应用前景。

本项目针对纳米碳基印迹功能材料普遍存在的分散性与固液分离性能之间的矛盾，提出两条解决策略：一是通过将光敏TiO2和疏油性的交联剂1H,1H,2H,2H-全氟癸基三氯硅烷，或者疏水性的交联剂3-（三甲氧基硅）甲基丙烯酸丙酯相复合，利用二者在不同光照条件下此消彼长的浸润性作用效果，实现了印迹材料表面浸润性可光响应切换的设计，并对光响应性浸润性可切换功能的实现机理进行了阐释。二是通过将零维粉体纳米碳材料同高维材料复合，或者直接以高维碳基材料（如碳气凝胶）为基质，制备获得二维纳米碳基复合薄膜或者三维印迹块体吸附材料，提高了材料的再生回收性能和实用性能。.通过这两方面的实验探索，制备了一系列用于油相脱硫与水相脱酚的碳基表面分子印迹材料（C-SMIP），在油品脱硫方面，针对目标分子DBT，分别获得了磁性C-SMIP，紫外光响应浸润性可切换的C-SMIP，以及二维碳基复合印迹薄膜吸附材料，对DBT的吸附量分别达到15.2，90.0和101.7 mg g-1；在水相脱酚方面，针对目标分子苯酚，分别获得了多孔碳纳米球基C-SMIP，紫外光响应浸润性可切换的中空C-SMIP，以及三维碳气凝胶基印迹块体吸附材料，对苯酚的吸附量分别达到85.7，113.7和63.9 mg g-1。进一步地，对此类C-SMIP材料的选择性识别吸附机理做出了深入探讨，推断出C-SMIP对于目标分子吸附的本质是固液界面间的物理性吸附，但利用分子印迹技术构建仅适用于目标分子的印迹空穴，可以使原本各向异性的多重作用力开始协同作用，从而对目标分子产生近似于化学吸附的强度和选择性，由此厘清了印迹材料吸附动力学和热力学过程的内在机制，解决了长时间以来令人困扰的对吸附过程定性的争议，为该领域中基质筛选、印迹方法构建、吸附条件优化等提供了一些有益的借鉴和启发。.