新型高效钌(II)配合物有机无机杂化氧气传感纳米纤维的静电纺丝制备及性能研究

The effetive synthesis method and technology to prepare inexpensive, high-performance novel organic/inorganic hybrid optical oxygen sensing nano-fibers will be explored from the viewpoints of the dispersibility of Ru(II) diimine complex, the oxygen diffusion rate and the stability of the luminore probe whinth the matrix. Then, the intrinsic correlation of the microenvironment controlling and the oxygen sensing properties will be investigated in this project. Utilizing the unique physical and chemical properties of matrix materials in which its microenvironment is easily tailored, and the bi-functional characteristic of the organic modified silicate ester, directional orientation of Ru(II) complexes on the nano-fibers materials can be obtained via the electrostatic spinning technology, and the micro-environment homogeneous distribution of Ru(II) probe molecules within the framework of the matrix will be achieved. Through this strategy, the signal-shifting problem caused by the leaking of probe complex due to the weak physical interation between the matrix and the luminophore will be solved. Obvious improvement in photo-thermal stability, long-term stability and reproducibility of the novel Ru(II) covalently grafted nano-fibers oxygen sensing materials will be expected. This research has important theoretical value and instructive significance to solve key problems about the transition metal Ru (II) diimine complexes hybrid oxygen sensing materials, and is helpful to understand the intrinsic relationship between the oxygen and the complex. Experimental evidences in the field of organic/inorganic hybrid optical oxygen sensing materials will be established for the fundamental and application researchs. The obtained novel optical oxygen sensing materials in the research of this project are expected to play an important role in monitoring and dectecting the oxygen content in these fileds such as industry, environment protection, and aquaculture.

围绕Ru(II)二亚胺配合物探针分子在基质中分散性；基质中氧气扩散速率；防止氧气传感信号漂移以及探针分子的团聚和脱落等问题研究低成本、高质量的新型高效有机/无机杂化光学氧传感纳米纤维的有效合成方法与技术。在此基础上研究杂化氧传感材料微环境的调控对性能的影响。.利用载体材料微环境便于调控的奇特物理化学性能，结合有机改性硅酸酯的配位能力以及可水解缩聚双功能特性，实现过渡金属Ru(II)探针分子在载体材料骨架内的微区均相化学组装，通过静电纺丝技术实现一维纳米纤维的定向取向，解决目前氧气浓度检测过程中所面临的配合物探针脱附难题，显著改善其信号稳定性、光热稳定性、延长使用寿命。本研究对于解决过渡金属Ru(II)配合物杂化氧气传感材料的关键问题，加深对该类氧气传感材料性能调控的理解和认识具有重要理论价值和指导意义。所形成的新型光学氧传感材料在工农业生产、环境保护、水体检测和监控等方面将会发挥重要作用。

本项目主要研究了共价嫁接Ru(II)二亚胺配合物硅基有机/无机杂化氧气传感材料的合成及性能。通过对1, 10-邻菲啰啉进行有机修饰，合成了一种可水解的有机改性硅酸酯，使其不但能够和过渡金属Ru(II)配位，而且能够与正硅酸乙酯进行水解和共缩聚反应制备共价嫁接的有机-无机杂化材料。我们的研究发展了一种制备共价嫁接Ru(II)二亚胺配合物为探针分子的有机/无机杂化功能材料的方法。以制得的有机改性硅酸酯为前驱体，在模板剂的结构导向作用下，制备了介孔硅基有机/无机杂化氧气传感材料。通过系统的研究发现，共价嫁接样品与物理包埋样品相比较，具有更短的响应时间，更高的灵敏度，以上优点可归因于独特的多孔结构有利于氧气在其中的扩散，并最终产生了快速的猝灭响应。此外共价嫁接样品具有优越的光化学稳定性，我们的结果表明通过水解和共缩聚反应把有机Ru(II)发光配合物共价嫁接到无机材料的骨架上，可以改善杂化材料的光辐照稳定性和抗脱附能力，所获得的光学氧传感介孔材料其性能可以通过改善载体的微相结构进一步提高，作为光学氧传感材料具有较大研究的潜力。.另外，我们还以荧光碳量子点为探针，获得了对氧气、重金属Hg2+离子具有传感响应的有机/无机杂化硅基介孔材料。作为本研究项目内容的拓展，我们进一步以碳量子点为探针分子，以PVA-SiO2为载体，通过静电纺丝方法制备出具有一维结构对重金属离子Hg2+有明显传感性能的有机/无机杂化材料。.此外，感谢本研究项目的支持，使我们能够在以前的工作基础上，继续开展无机长余辉发光材料方面的研究，并取得了一些结果，获得了两种Eu2+掺杂的蓝绿色长余辉发光材料，包括Ca8Mg(SiO4)4Cl2:Eu2+和BaAlSi5N7O2:Eu2+，均得到了纯度较好的长余辉发光材料。