光响应分子非对称修饰及协同调控纳米通道离子输运性能研究

Energy and environmental crises have become the most urgent problems in human society. Learning from nature is the eternal theme of the development of novel energy conversion materials and devices. Through hundreds of millions years of evolution, photosynthesis of plants exhibits almost the best efficiency of natural process, which is dependent on the complex system that composed by the integration of the molecules and assemblies with different functions. However, each previously constructed biomimetic light-responsive nanochannel is only focused on studying one kind of molecules and endowing these artificial nanochannels with greater intelligence is still a challenging task. Inspired by photosynthesis, the environment-friendly hourglass shaped alumina nanochannels with stable performane would be firstly constructed for asymmetric modifiying of light-responsive molecues, which would induce the heterogeneous surface/interface on inner walls for exhibiting the cooperative effect of the structure and function of the molecules. Under light irradiation, the surface chare intensity, polarity or distribution would be altered of the modificated alumina nanochannel inner walls, which would regulated the ionic tranported properties. Based on these behaviors, we would succeed in developing the smart nanochannels that based on the coopertive responsive principle including configuration-change/photoelectircal-conversion and synergistic photoelectircal-conversion effect, and further producing the light- and pH-gating channels over the asymmetirc dual control. The more system and excellent ionic transport performance would be obtained in this project than the using of one kind of light-responsive molecule modified nanochannels. This project could provide new materials and principles for the development of novel biomimetic nanochannel energy conversion devices.

能源和环境危机已成为摆在全人类面前最亟待解决的问题。向自然学习是能量转换新材料和新器件发展的永恒主题。植物光合作用是亿万年进化中最高效的自然过程，其原理在于将具有不同功能的分子及集合体衔接成一个系统。然而，已有的仿生光响应纳米通道是基于对单种分子的研究，难以实现更多更复杂的光响应性功能。受光合作用启发，本项目以绿色环保、性能稳定的沙漏形氧化铝纳米通道为研究对象，在孔道内非对称修饰两种光响应分子，利用异质分子结构和响应特性的协同互补，引起光照下孔道内电荷密度、极性或分布发生变化，导致离子输运性能改变，实现基于构型变化/光电转换、协同光电转换作用原理的智能化纳米通道，并进一步产生非对称光与pH双响应的孔道开关。获得比使用单种光响应分子的纳米通道更加系统及优异的离子输运性能，这将为开发和设计仿生纳米通道能量转换器件提供新材料和新原理。

自然界丰富的能量转换系统为人类开发可再生能源提供有价值的借鉴。其中，膜蛋白离子通道扮演了重要角色。但这种离子通道的功能只能在脂质环境中发挥作用。仿生纳米通道体系的构建弥补了这些不足。因而，设计和构筑基于光捕获的仿生纳米通道能量转换材料和器件成为近年来的研究热点之一。本课题的研究目的是在深入了解光响应分子的作用机理后，致力于探究异质材料的结构对功能的影响，并进一步研究通道组成、结构、离子输运性能三者的关系。本课题所设计和制备的光响应纳米通道，既具有创新性，又具有重要的科学意义和应用前景，为设计和制备新一代高效能量转换体系及器件提供了一种新的方法和研究思路。.受植物光合作用中光系统I和II协同互补的启发，如何赋予光响应的仿生纳米通道更多更复杂的光响应性功能，将是一项具有创新性和挑战性的工作。本课题的研究内容是如何利用光响应分子组成及通道结构变化提高光捕获效率并且研究其对离子跨膜输运行为的调控变化规律。基于此，本课题的研究目的就是在深入了解光响应分子的作用机理后，充分利用通道的结构效应和光响应分子多功能化的反应界面，控制离子输运性能、智能响应性能及能量转换规律，实现更系统、更优异的能量转换器件及光控开关。在具体的研究过程中，通过改进的阳极氧化法制备了带有限域空间的多孔氧化铝纳米通道；利用溶液扩散限制修饰方法，构筑了异质光响应分子非对称修饰的光响应纳米通道，获得了“暗态-可见光-紫外光”刺激响应的三元可控开关；实现了双光响应分子协同增强的光电效应；产生了非对称光与pH双响应的智能开关；进一步，我们利用光响应分子自组装成纤维结构，获得了复合结构的纳米通道，提高了光响应离子电流至微安级；此外，我们还研究了复合通道光照增强的盐差发电行为。本项目所获得的光响应纳米通道及其相关性能，为开发和构筑高效仿生纳米通道能量转换体系提供了积极的支撑作用。