基于光诱导给-受体界面电位梯度的仿生纳米通道能量转换体系

For the purpose of development and utilization of the efficient clean energy, the bionic nanochannels energy conversion system has recently been promoted upon the joint effect between light-responsive molecules and other materials or the cooperative property of two kinds of light-responsive molecules. Inspired by perfect integrated system in plant photosynthesis constituted by the microstructure and the function, in this project, we will fabricate the funnel-shaped alumina nanochannels, and adopt thiophene polyelectrolytes as electron donors and light-responsive small organic molecules as electron acceptors, which will be assembled into the alumina nanochannels in two ways for forming the donor-accepter heterogeneous surface/interface with a two-dimensional or three-dimensional continuously distributed characteristic. Under light irradiation, the potential gradient at the donor-acceptor interface will be generated resulting in the charge separation in donor-accepter, which will lead a change of the charge density and polarity on nanochannels inner surface. The light-regulated smart switch and the increased ion current or ion rectification ratio will be successfully obtained. In this project, the biometric nanochannels will be constructed based on the integration effect combined with the structural characteristic of the funnel-shaped nanochannels and the cooperative property of the donor and acceptor, which will show more superior performance and more systematic intelligent response than previously reported work. Further, the excited state energy of the donor-acceptor molecules will be directly transferred to the quinone/hydroquinone redox pair in solution and light energy will be converted into electric/chemical energy in this process. Our constructed nanochannels energy conversion system will move one small step further towards mimicking the complex photosynthesis mechanisms, and will play a positive role in promoting efficient nanochannels energy conversion devices.

以开发和利用高效清洁能源为最终目的，仿生纳米通道能量转换体系的构筑已发展为利用光响应分子与异质材料融合或与其它光响应分子协同作用。受植物光合作用结构和功能完美集成系统的启发，本申请将以漏斗形氧化铝纳米通道作为研究媒介，以噻吩聚电解质作为电子给体，有机光响应小分子作为电子受体，采用两种方式进行通道内组装，形成面或空间连续分布的给-受体异质表/界面，光照诱导界面电位梯度产生引起电荷分离，导致通道表面电荷密度、极性等发生改变，获得光控智能开关及光致增大的离子电流、离子整流比。实现基于通道结构效应和分子协同效应一体化作用的仿生纳米通道，呈现更加优异的性能和更加系统的智能响应。并进一步将激发态的能量传递给溶液中的醌/氢醌氧化还原对，完成光能到电能/化学能的转换, 把对自然机理的模拟向前推进一小步，这将为实现高效纳米通道能量转换器件起到积极的促进作用。

太阳能是维持生命系统的基本能源。构建人工纳米通道能量转换体系，来模拟植物光合作用中结构与功能的一体化作用，是一项具有创新性和挑战性的工作。从生物离子通道出发，去完成仿生纳米通道的设计和研究，国内外课题组已做出一些开创性的研究工作。而将光响应分子与异质材料的融合或与其它光响应分子的协同作用，将产生更加复杂和系统的智能化光调控，获得更加高效的能量转换器件。本课题以开发高效仿生纳米通道能量转换体系为研究目的，以氧化铝纳米通道作为研究媒介，将光响应分子间的协同作用与通道结构进行有效融合，研究界面电位梯度的产生和界面组装关联规律，提升光捕获效率和激子（电子-空穴对）分离效率，并进一步引入醌-氢醌氧化还原对，调控跨膜载体输运行为。探索纳米通道的微观结构与多功能化反应界面一体化作用的微观作用原理及能量转换规律。在具体的研究过程中，我们构建了基于N3/SP-COOH协同光响应的纳米通道，实现比单独修饰一种分子更高的离子选择性和光响应性。通过PTE-BS/N3纳米通道获得面-面接触的界面电位梯度，促进异质分子光响应电子-空穴对的有效分离，使光响应电流的变化达到100%。并通过PT2-N3(T)功能化的纳米通道，获得空间连续接触的界面电位梯度，进一步使这一比率提高到128％。同时，基于卟啉和酞菁组装体的纳米通道（TPPS/Al2O3、ZnTspc/Al2O3和FeTmpyp/Al2O3）不仅提供了高的稳定性，还实现了界面电位梯度对仿生纳米通道光电转换性能的增强作用，并把光能从原初受体分子传递到醌-氢醌（Q-H2Q）氧化还原对，提升体系开路电压和短路电流，把对光合作用自然机理的模拟向前推进了一小步。更进一步将纳米通道应用于对光能和渗透能的协同捕获，获得2.16 W/m2（暗态）和4.56 W/m2（光照）的输出功率，并在界面电位梯度的协助下，将其分别提高到12和13 W/m2。这将为基于光电转换性能的仿生纳米通道的设计和构筑探寻到积极的、潜在的应用方向。经过本课题的研究，将为最终实现仿生纳米通道的智能调控和能量转换应用提供直接的、有价值的实验借鉴。